Ligated transition metal derivatives of heteropolyanions

ABSTRACT

Salts and acids containing a triheteropolyanion in which one addenda atom of a heterododecatungstate or heterododecamolybdate is replaced by one tin atom or by two germanium atoms, in which the tin atom or the germanium atoms are bonded to a ligated transition metal, have outstanding utility as catalysts for the oligomerization of terephthalic acid with ethylene glycol, and for the isomerization of 1-butene, and for the dehydration of 2-butanol and subsequent isomerization of the 1-butene formed.

TECHNICAL FIELD

This invention relates to compounds containing transition metalderivatives of heteropolyanions.

BACKGROUND ART

Heteropolyanions are familiar chemical entities, and a great variety ofacids and salts containing them are known. They are reviewed, forexample, by Baker in "Advances in the Chemistry of the CoordinationCompounds", Kirschner, Ed., p 604 (MacMillan, 1961); by Evans in"Perspectives in Structural Chemistry", Vol. IV, Dunitz and Ibers, Ed.,p 1 (Wiley, 1971); by Weakley in "Structure and Bonding", Vol. 18, p 131(Springer-Verlag, 1974); and by Sasaki and Matsumoto in J. Japan, Chem.,29, 853 (1975).

Typical heteropolyanions are dodecatungstosilicate or12-tungstosilicate, SiW₁₂ O₄₀ ⁴⁻, and dodecamolybdophosphate or12-molybdophosphate, PMo₁₂ O₄₀ ³⁻. In these anions the silicon andphosphorus atoms are usually designated as "central" atoms and thetungsten and molybdenum atoms are referred to as "addenda" atoms (Baker)or "peripheral" atoms (Chemical Abstracts). Molybdenum, tungsten, andvanadium are the most common addenda atoms. About 45 other elements,including most transition metals, can function as central atoms.Tungstosilicates and molybdophosphates are frequently referred to alsoas silicotungstates and phosphomolybdates and are sometimes formulatedas, for example, W₁₂ SiO₄₀ ⁴⁻ and Mo₁₂ PO₄₀ ³⁻.

Heteropolyanions are most stable in solutions of relatively low pH. Itis known that by raising the pH, an addenda atom and one accompanyingoxygen atom can be removed selectively from certain heteropolyanions(e.g., a WO⁴⁺ moiety from SiW₁₂ O₄₀ ⁴⁻). By a number of methods, thecavity then present in the heteropolyanion cage can be filled by adifferent atom, such as chromium, manganese, iron, cobalt, nickel,copper, or gallium. See, for example, Baker et al., J. Am. Chem. Soc.,88, 2329 (1966); Weakley and Malik, J. Inorg. Nucl. Chem., 29 2935(1967); and Tourne et al., Bull. Soc. Chem., 1969, 1124, and J. Inorg.Nucl. Chem., 32, 3875 (1970).

The anions resulting from these "substitutions" are frequentlydesignated in abbreviated fashion as, for example, XZW₁₁, where X is theoriginal, central or "inner" hetero atom and Z is the new, "outer"hetero atom. X has also been used to designate a pair of atoms, i.e.,hydrogen atoms. These "substituted" heteropolyanions have been referredto as triheteropolyanions, in accordance with the presence of threedifferent kinds of positive-valent atoms. Baker and Figgis, J. Am. Chem.Soc., 92, 3794 (1970) and Weakley, J. Chem. Soc. Dalton, 1973, 341, haveshown that an outer hetero atom in such a heteropolyanion can be bondedto a ligand such as water, pyridine, or halide ion. These conclusionshave been disputed by Komura et al, Bull. Chem. Soc. Japan, 49 (1), 87(1976).

In the field of transition metal chemistry, a large number of compoundsare known in which ligated transition metals are bonded directly toligated Group IVb elements other than carbon, e.g., silicon, germanium,and tin. A review article published in 1970 reports that the number ofsuch compounds had risen from a few dozen in the early 1960's to morethan 500; see Brooks and Cross, Organometal. Chem. Rev. A, 1970, 227.Many more such compounds have been reported since 1970.

Regarding the ligands bonded to transition metals in such compounds,Brooks and Cross point out that in general the same ligandconfigurations that give stable organo transition metal complexes alsogive stable group IVb metal derivatives. For example, the configurationπ-C₅ H₅ (CO)₂ Fe-- is a common one; stable compounds are known in whichit is bonded to itself, to halogen, to hydrocarbyl, and to metals suchas sodium and mercury. Correspondingly, Brooks and Cross list a numberof stable compounds in which the π-C₅ H₅ (CO)₂ Fe-- grouping is bondedto silicon, germanium, or tin, the Group IVb atom being bonded in turnto ligands such as halo or hydrocarbyl. In addition toπ-cyclopentadienyl and carbonyl, other ligands that are bonded totransition metal compounds in the many examples listed by Brooks andCross include π-benzene, phenanthroline, bipyridine, phenyl,trihydrocarbylphosphine, trihydrocarbyl phosphite,trihydrocarbylstibine, dihydrocarbyl sulfide, trihydrocarbylarsine,cyano, cyclooctadiene and norbornadiene.

DISCLOSURE OF INVENTION

The products of the present invention are salts and acids eachcontaining a triheteropolyanion in which one addenda atom of aheterododecatungstate or heterododecamolybdate is replaced by one tinatom or by two germanium atoms, each of which tin or germanium atoms isbonded to a ligated transition metal atom.

The products of the invention have the following distinguishingcharacteristics:

1. The original hetero atom, i.e., the central atom, of theheterododecaanion does not become bonded directly to a new enteringgroup, in particular to a ligated transition metal-tin or -germaniummoiety.

2. The added ligated transition metal is not part of the dodecanuclearcage structure.

3. The heteropolyanion contains at least one metal-metal bond, which isoutside the skeletal structure of the heteropolyanion.

The products of the invention can be grouped by formulas into severaldifferent types.

Products of type 1 have the formula

    [Q.sup.+ ].sub.a ]L.sub.b MSnM'.sub.11 XO.sub.39 ].sup.a-  ( 1)

Formula (1) is written to bring out the ionic nature of the product. Itcan also be written simply as Q_(a) L_(b) MSnM'₁₁ XO₃₉.

In formula (1)

Q⁺ is one equivalent of a cation;

the moiety L_(b) M comprises a ligated transition metal M bonded to bligands L, b is at least 1, and the ligands can be the same or differentwhen b is greater than 1;

M' is W or Mo;

X is Si, P, Co, or Ge; and

a is the number of formal negative charges on the heteropolyanion L_(b)MSnM'₁₁ XO₃₉, and is usually 4-8. When "a" is greater than 1, the Q'scan be the same or different.

As will be apparent from the examples, the products of this inventionare usually prepared in aqueous or partly aqueous media and are mostreadily isolated as hydrates corresponding to various degrees ofhydration. These hydrates are included in the invention and,accordingly, the claims should be interpreted as including hydrates ofthe claimed products.

Suitable products of type 1 include

[(CH₃)₄ N]₅ (CO)₄ CoSnW₁₁ SiO₃₉,

[(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉,

[(CH₃)₃ NH]₅ π-C₅ H₅ Ru(CO)₂ SnW₁₁ SiO₃₉,

[(CH₃)₃ NH]₅ (dimethylglyoxime)₂ Co(NC₅ H₅)CoSnW₁₁ SiO₃₉,

K₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉,

[(CH₃)₄ N]₅ p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnW₁₁ SiO₃₉,

[(CH₃)₄ N]₅ C₆ H₅ Pt[PC₂ H₅)₃ ]₂ SnW₁₁ GeO₃₉,

[(CH₃)₃ NH]₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉,

[(CH₃)₃ NH]₅ π-C₅ H₅ Ni(CO)SnW₁₁ GeO₃₉,

K₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉,

[(CH₃)₄ N]₅ π-C₅ H₅ W(CO)₃ SnW₁₁ SiO₃₉,

[(CH₃)₄ N]₅ π-C₅ H₅ Mo(CO)₂ P(C₆ H₅)₃ SnW₁₁ SiO₃₉,

K₈ (CO)₃ Co(SnO₃)SnW₁₁ PO₃₉,

[(CH₃)₄ N]₇ π-C₅ H₅ Fe(CO)₂ SnW₁₁ CoO₃₉,

[(CH₃)₄ N]₇ (n-C₄ H₉)₃ PCo(CO)₃ SnW₁₁ CoO₃₉,

[(CH₃)₄ N]₅ (CO)₂ Fe(NO)[P(C₆ H₅)₃ ]SnW₁₁ SiO₃₉,

[(CH₃)₄ N]₅ (C₆ H₅ O)₃ PFe(CO)₂ (NO)SnW₁₁ GeO₃₉,

[(CH₃)₃ S]₄ [H]π-C₅ H₅ Fe(CO)₂ SnMo₁₁ SiO₃₉,

[(CH₃)₃ S]₄ [H]π-C₅ H₅ Mo(CO)₂ P(OCH₃)₃ SnMo₁₁ SiO₃₉,

[(CH₃)₃ S]₄ [H]π-C₅ H₅ Ru(CO)₂ SnMo₁₁ SiO₃₉,

[(CH₃)₃ S]₄ [H][(C₆ H₅)₂ PCH₂ CH₂ P(C₆ H₅)₂ ]₂ Re(CO)SnMo₁₁ SiO₃₉,

[(CH₃)₄ N]₁₀ SnW₁₁ SiO₃₉ Co(CO)₃ SnMo₁₁ SiO₃₉,

[(CH₃)₃ NH]₄ (C₇ H₈)₂ RhSnW₁₁ PO₃₉,

[(CH₃)₃ NH]₅ (CH₇ H₈)₂ IrSnW₁₁ SiO₃₉,

[(CH₃)₃ NH]₅ [(C₆ H₅)₃ As]₂ C₈ H₁₂ IrSnW₁₁ GeO₃₉,

[(CH₃)₃ NH]₅ C₇ H₈ Co(CO)₂ SnW₁₁ SiO₃₉,

[(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ GeO₃₉,

[(CH₃)₃ NH]₄ [(C₆ H₅)₃ P]₂ C₇ H₈ RhSnW₁₁ PO₃₉,

[(CH₃)₃ NH]₅ (C₆ H₅)₃ P(π-C₃ H₅)PdSnW₁₁ SiO₃₉,

K₅ [(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnW₁₁ SiO₃₉,

Ba₅ [π-C₅ H₅ Mo(CO)₂ P(OCH₃)₃ SnW₁₁ GeO₃₉ ]₂,

[(C₂ H₅)₄ As]₄ π-C₅ H₅ Ru(CO)₂ SnW₁₁ PO₃₉,

Li₅ π-C₅ H₅ Ni(CO)SnW₁₁ SiO₃₉,

Zn₇ [(C₇ H₈)Co(CO)₂ SnW₁₁ CoO₃₉ ]₂,

Cs₅ (C₆ H₅ O)₃ P(NO)(CO)₂ FeSnMo₁₁ GeO₃₉,

K₄ [(C₆ H₅)₃ As](CO)₃ CoSnW₁₁ PO₃₉,

H₅ [(C₆ H₅)₃ P](CO)₃ CoSnW₁₁ GeO₃₉,

and their hydrates.

The sole function of Q in compounds of formula (1) is to provide acounter-ion or -ions for the novel heteropolyanion, which is the essenceof the invention. To put it another way, the sole purpose of Q is toprovide a means for isolating the novel heteropolyanion in compoundform. The properties of Q, therefore, are not critical and Q canrepresent a broad range of elements or combination of elements. Only onelimitation on the very broad nature of Q is known. Since the products ofthe invention are made and frequently used in the presence of water, thecation Q should be reasonably stable to water.

Because of availability and ease of preparation of new productscontaining them, preferred values of Q are hydrogen, alkali metal, oneequivalent of alkaline-earth metal, NH₄, RNH₃, RR'NH₂, RR'₂ NH, RR'₃ N,R₄ P, R₃ S, R₄ As, or R₄ Sb, wherein R' is aliphatically saturatedhydrocarbyl bonded to N through aliphatic carbon and contains up to 18carbons and preferably up to 12 carbons, and R is aliphaticallysaturated hydrocarbyl of up to 18 carbons and preferably up to 12carbons. Any two R and R' groups in the same cation can also be joined(bonded) to each other directly or through an ethereal oxygen atom toform a divalent, aliphatically saturated hydrocarbyl oroxygen-interrupted (mono-oxa) hydrocarbyl group of up to 18 carbons andpreferably up to 12 carbons. Most preferably this divalent group isalkylene of 4-8 carbons. "Aliphatically saturated hydrocarbyl" isdefined as hydrocarbyl that does not contain any ethylenic or acetyleniccarbon-carbon unsaturation, i.e., the hydrocarbyl groups can be alkyl,cycloalkyl, aryl, alkaryl, or aralkyl. Thus the term refers tohydrocarbyl in which any unsaturation is aromatic.

Examples of the Q cations as defined above include hydrogen, sodium,potassium, rubidium, barium, calcium, strontium, magnesium, cesium,ammonium, methylammonium, cyclopropylammonium, 1-methylheptylammonium,2-(1-naphthyl)ethylammonium, octadecylammonium, p-ethylanilinium,diisobutylammonium, dicyclohexylammonium, dinonylammonium, morpholinium,dodecamethyleniminium, triisopropylammonium, N-methylpiperidinium,trihexylammonium, dodecyldimethylammonium, tetraisopentylammonium,heptyltrimethylammonium, trimethylpentylammonium,cyclodecyltrimethylammonium, N,N-didodecylmorpholinium,dimethylanilinium, tetramethylphosphonium, tetranaphthylphosphonium,ethylpentamethylene-p-tolylphosphonium, dimethyloctadecylsulfonium,methyltetramethylenesulfonium, triethylsulfonium, tetraphenylarsonium,benzylhexadecyldimethylarsonium, dodecyltriethylarsonium,tetramethylstibonium, dibenzyldimethylstibonium, and the like.

Of the above R- and R'-substituted cations, those containing only loweralkyl (1-6 carbons) are preferred, especially tetramethylammonium andtrimethylammonium. The latter are useful precipitating cations to giveproducts containing the novel heteropolyanions in readily isolable form.Preferred cations overall are hydrogen, the alkali metals, and the onesin the first sentence of this paragraph.

Compounds of the invention in which Q is hydrogen are ordinarilyisolated as solvates. Since these compounds are most commonly workedwith in aqueous media, the most common types of solvates are hydrates.The exact position of attachment of the solvate molecules is not known,but at least some of them are almost certainly associated with thehydrogen ions. It is to be understood, therefore, that the term"hydrogen" as used here, includes, and in fact for all practicalpurposes always refers to, hydrogen ions solvated with water or othersolvent molecules. When Q is hydrogen, the degree of solvation of thehydrogen ion is of no particular importance to the present invention.The above usage of the term "hydrogen" is based on nomenclature approvedby the International Union of Pure and Applied Chemistry; see J. Am.Chem. Soc., 82, 5529-30 (1960).

As noted above, the ligand configurations in the ligated transitionmetal moiety L_(b) M, i.e., the nature of L and the value of b, willgenerally be the same as those that give stable complexes of theparticular transition metal generally. Most specifically and forexample, Brooks and Cross point out that in transition metal-Group IVbmetal compounds the coordination sphere of chromium, molybdenum, ortungsten always includes a combination of π-bonding ligands. Commonexamples are combinations of π-benzene, π-cyclopentadienyl, orbipyridine with carbonyl. For manganese and rhenium the ligands arealmost without exception carbonyls. With iron, ruthenium, and osmium theligands are most frequently carbonyls or combinations of carbonyl withπ-cyclopentadienyl. With metals of the cobalt group, compoundscontaining cobalt itself tend to contain carbonyl and cyclopentadienylcarbonyl ligands with properties comparable to those of manganese andiron; ligands attached to rhodium and iridium compounds tend more to betertiary phosphines, arsines, and stibines, halide, hydride, andcyclopolyene ligands. Nickel compounds usually involve carbonyl orπ-cyclopentadienyl ligands, whereas palladium and platinum derivativestend more to phosphine, cyano, and cyclopolyene ligands. Overall theligated transition metal moieties that will be operable will be quitefamiliar to one skilled in the art, particularly after a review of theBrooks and Cross article and of later publications on this subject. Theforegoing illustrations are not intended to be limiting; in general anyligand, L, that can be present in a ligated transition metal-tintrihalide or -germanium trihalide can be present in a product of theinvention.

From the foregoing discussion it will be seen that L can be a neutralligand such as π-benzene, carbonyl, bipyridine, and phosphine or aligand with a formal valence of -1 such as π-cyclopentadienyl, halideand hydride. A bidentate ligand such as bipyridine will be theequivalent of two L's.

The number of formal negative charges, a, on the novel heteropolyanionis of course the algebraic sum of the oxidation states of all the atomsin the anion. For example, in the heteropolyanion, [(CO)₄ CoSnW₁₁ SiO₃₉]⁵⁻, of the product of Example 1 each oxygen is in an oxidation state of-2, each tungsten +6, and the silicon +4. The tin is assumed to beformally +4 (Brooks and Cross, page 38), and the cobalt is assigned -1,corresponding to its oxidation state in HCo(CO)₄. The four carbonylgroups are assumed to be neutral and not contribute formally to thecharge on the heteropolyanion. The algebraic sum of the oxidation statesof the one cobalt, one tin, one silicon, eleven tungstens andthirty-nine oxygens is -5, corresponding to the five tetramethylammoniumcations present in the product.

One skilled in the art will be aware that because of the sometimescomplex interactions between the various atoms of large anions of thistype, the presence of metal-metal bonds, the variable oxidation statesof transition metals, and the known uncertainties regarding oxidationstates in some transition metal complexes, assignment of oxidationstates in some instances will have to be rather arbitrary. Although theoverall formal charge on the heteropolyanion in products of theinvention can usually be accurately predicted and calculated, the bestmethod of determining this charge is probably the empirical one offinding out the number of cation equivalents present via analysis.

Products of type 1 in which X is Si, Ge or P are made by reacting aligated transition metal-tin trichloride, L_(b) M-SnCl₃, with a salt oracid containing the heteropolyanion of composition M'₁₁ XO₃₉. As notedpreviously, the latter reactant is made by raising the pH of a solutionof a compound containing the corresponding M'₁₂ XO₄₀ anion, by whichprocess an M'O entity is removed. The M'₁₁ XO₃₉ -containing reactant canbe prepared and isolated in advance; see preparation of K₈ W₁₁ SiO₃₉below and its use in several examples. Alternatively the M'₁₁ XO₃₉-containing reactant can be prepared and used in place withoutisolation. Tribromides or triiodides can be used in place of thetrichlorides L_(b) M-SnCl₃.

Compounds of type 1 in which X is Co are prepared by a correspondingreaction with a salt or acid containing the heteropolyanion ofcomposition Co₂ M'₁₁ O₃₉.H₂ O. In these heteropolyanions one cobalt isthe central, inner hetero atom and the other is the twelfth atom of theheterododecaanion cage.

A rather specialized method for making a small group of compounds oftype 1 is discussed below in connection with products of type 2.

Products of type 1 are usually isolated from aqueous reaction mixturesby addition of a "precipitating" cation, i.e., a cation that forms arelatively insoluble salt with the novel heteropolyanion in solution.Examples of such cations are tetramethylammonium, trimethylammonium, andtrimethylsulfonium. Products of the invention containing cations otherthan these precipitating cations can be made from the primary productsby conventional cation-exchange methods.

In most of the reactions involved in the preparation of type 1 productsof the invention and products of other types discussed below, theligated transition metal moiety L_(b) M persists unchanged, and thereaction is essentially a straightforward insertion/metathesis. For afew L_(b) M moieties, however, under certain conditions which cannotreadily be predicted in advance, one ligand, L, is partly or entirelylost by the transition metal, and its place is taken by atriheteropolyanion moiety, SnM'₁₁ XO₃₉. The products of the inventionthus formed, designated type 2, have as an overall anionic component astructure in which two heteropolyanion moieties, each with tin as a newaddenda atom, are bonded through the tins to a ligated transition metalatom. These products can be represented by the formula

    [Q.sup.+ ].sub.a [L.sub.b-1 M(SnM'.sub.11 XO.sub.39).sub.2 ].sup.a-, (2)

which also can be written simply as Q_(a) L_(b-1) M(SnM'₁₁ XO₃₉)₂. Theterms in these formulas are defined as for formula (1), except that b isat least 2 and a is usually 9-11; the considerations noted for formula(1) also apply.

Each SnM'₁₁ XO₃₉ moiety of a product of type 2, and therefore theoverall anionic portion of such a product, has the three characteristicsof a product of the invention listed above.

Suitable products of type 2 include

[(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂,

H₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂,

K₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂,

Na₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂,

[(CH₃)₃ NH]₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂,

K₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂,

[(CH₃)₃ NH]₁₁ (CO)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂,

K₁₁ (CO)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂,

[(CH₃)₃ NH]₁₁ π-C₃ H₅ Pd(SnW₁₁ SiO₃₉)₂,

Na₁₁ (CO)₃ Co(SnW₁₁ GeO₃₉)₂,

K₉ (CO)₂ (NO)Fe(SnW₁₁ GeO₃₉)₂,

and their hydrates.

As noted above, products of type 2 are prepared by reacting particularligated transition metal-tin trichlorides, L_(b) M-SnCl₃, with a salt oracid containing the heteropolyanion of composition M'₁₁ XO₃₉. Example 15illustrates preparation of a product of type 1 by reacting a type 2product with potassium cyanide. In this reaction one of the SnW₁₁ PO₃₉³⁻ moieties bonded to cobalt becomes replaced by the L-type ligand SnO₃³⁻.

Products of the invention of type 3 can be represented by the formula

    [Q.sup.+ ].sub.a [(L.sub.b MGe).sub.2 M'.sub.11 XO.sub.40 ].sup.a-, (3)

which can also be written simply as Q_(a) (L_(b) MGe)₂ M'₁₁ XO₄₀. Theterms in these formulas are defined as for formula (1) and theconsiderations noted for formula (1) again apply. In addition, eachproduct of type 3 has the three characteristics of a product of theinvention listed above.

Suitable products of type 3 include

[(CH₃)₃ NH]₄ [π-C₅ H₅ Fe(CO)₂ Ge]₂ W₁₁ SiO₄₀,

[(CH₃)₃ NH]₃ [π-C₅ H₅ Fe(CO)₂ Ge]₂ W₁₁ PO₄₀,

[(CH₃)₃ NH]₃ [(C₆ H₅)₃ PCo(CO)₃ Ge]₂ W₁₁ PO₄₀,

[(CH₃)₃ NH]₄ [(C₆ H₅)₃ AsCo(CO)₃ Ge]₂ W₁₁ SiO₄₀,

[(CH₃)₃ NH]₄ [π-C₅ H₅ (C₂ H₅)₃ PNiGe]₂ W₁₁ GeO₄₀,

[(CH₃)₃ NH]₄ [π-C₅ H₅ Fe(CO)₂ Ge]₂ Mo₁₁ SiO₄₀,

Cs₄ [π-C₅ H₅ (CO)NiGe]₂ W₁₁ SiO₄₀,

(NH₄)₄ [π-C₅ H₅ (CO)₂ FeGe]₂ W₁₁ GeO₄₀,

[(C₂ H₅)₂ NH₂ ]₃ [(C₆ H₅)₃ P(CO)₃ CoGe]₂ W₁₁ PO₄₀,

and their hydrates.

Products of type 3 are made by reacting a ligated transitionmetal-germanium trichloride, L_(b) M-GeCl₃, with a salt or acidcontaining the heteropolyanion composition M'₁₁ XO₃₉. Tribromides ortriiodides can be used in place of the trichlorides.

Products of type 4 can be represented by the formula

    [Q.sup.+ ].sub.a [L.sub.b M(GeOH).sub.2 M'.sub.11 XO.sub.39 ].sup.a-, (4)

which also can be written simply as Q_(a) L_(b) M(GeOH)₂ M'₁₁ XO₃₉. Theterms in these formulas are defined as for formula (1), and theconsiderations noted for formula (1) again apply. Suitable products oftype 4 include

[(CH₃)₃ NH]₄ π-C₅ H₅ Co(CO)(GeOH)₂ W₁₁ SiO₃₉,

[(CH₃)₃ NH]₄ π-C₅ H₅ Co(CO)(GeOH)₂ W₁₁ GeO₃₉,

[(CH₃)₃ NH]₃ (C₆ H₅ NC)₂ Pd(GeOH)₂ W₁₁ PO₃₉,

K₃ (C₆ H₅ NC)₂ Pd(GeOH)₂ Mo₁₁ PO₃₉,

and their hydrates.

Products of the invention of type 5 can be represented by the formula

    [Q.sup.+ ].sub.a [L.sub.b M(SnM'.sub.11 XO.sub.39)(SnM".sub.11 X'O.sub.39)].sup.a-.                                      (5)

which can also be written simply as Q_(a) SnM'₁₁ XO₃₉ L_(b) MSnM"₁₁X'O₃₉. The terms in these formulas are defined as for formula (1), andthe considerations noted for formula (1) again apply. M" is defined thesame as M', and X' is defined the same as X; at least one of M" and X'is different from M' and X, respectively. M is preferably Co. It will beapparent that these products are quite similar to type 2, the differencebeing that the two heteropolyanion structures bonded through tin to aligated transition metal are different instead of the same. Suitableproducts of type 5 include [(CH₃)₄ N]₁₀ (SnW₁₁ SiO₃₉)Co(CO)₃ (SnW₁₁PO₃₉).

When the ligated transition metal-containing starting material used toprepare a product of the invention is a germanium trichloride (ortribromide or triiodide), L_(b) M-GeCl₃, in which the L_(b) M moiety isone of those that leads to a product of type 2 with tin-containingcompounds, then the factors operating in the formation of both type 2and type 3 compounds become involved, and reaction with an acid or saltcontaining a heteropolyanion of composition M'₁₁ XO₃₉ gives a polymericproduct (type 6) that can be represented by the formula

    {[Q.sup.+ ].sub.a [L.sub.b-1 MGe.sub.2 M'.sub.11 XO.sub.40 ].sup.a- }.sub.y,                                                  (6)

or more simply as (Q_(a) L_(b-1) MGe₂ M'₁₁ XO₄₀)_(y). The terms in theseformulas are defined as for formula (1), and the considerations notedfor formula (1) again apply. The value of y, the degree ofpolymerization, can be of the order of up to about 500. The actualrepeating unit in the polymeric structure is the novel heteropolyanionicmoiety L_(b-1) MGe₂ M'₁₁ XO₄₀. A cationic moiety Q_(a) is associatedwith each such heteropolyanionic moiety, but the latter moieties arebonded directly to each other, not through the Q_(a) moieties. Suitableproducts of type 6 include {[(CH₃)₃ NH]₅ (CO)₃ CoGe₂ W₁₁ SiO₄₀ }_(y).

The products of the invention can undergo ligand-displacement reactions,in which one or more L ligands are replaced by other types of L ligandsto give different products of the invention. An illustrative preparativereaction of this type is shown in Example 26.

BEST MODE

The following examples illustrate the products of the invention. Alltemperatures are in °C.

Starting materials not available commercially were prepared as follows:

K₈ W₁₁ SiO₃₉ Hydrate

Na₄ W₁₂ SiO₄₀ hydrate (13 g) in water (40 ml) was heated to 90°. Asolution of potassium acetate (15 g) in water (20 ml) was brought to pH7.0 with acetic acid, heated to 90° and added to the first solution. Themixture was stirred for five minutes at 90° and then filtered hot. Thesolid on the filter was 12.75 g of K₈ W₁₁ SiO₃₉.10H₂ O. Part of a lotprepared similarly but on a larger scale was analyzed:

    ______________________________________                                          Anal. Calcd for K.sub.8 W.sub.11 SiO.sub.39 . 10H.sub.2 O: K, 9.88;         Si, 0.88; 0, 24.75; W, 63.85; H.sub.2 O, 5.69                                 Found: K,      10.0;    Si,  0.55; 0, 24.41; W, 63.14;                                       9.6           0.52                                                                          0.86                                                                          0.88                                                    H.sub.2 O,                                                                            5.87                                                                          5.87                                                           ______________________________________                                    

In some preparations tungstosilicic acid was used in place of its sodiumsalt with no significant difference in the result.

(CO)₄ CoSnCl₃

This was prepared by two methods. The first is described by Patmore andGraham, Inorg. Chem., 7, 771 (1968). The second is mentioned, withoutdetails, by Ogino and Brown, Inorg. Chem., 10, 517 (1971). The followingprocedure was developed based on the brief mention by Ogino and Brownand is the preferred method because of higher yield.

Sodium amalgam was prepared from 99 g of mercury and sodium (1 g) in anitrogen atmosphere. Tetrahydrofuran (200 ml) was added, followed bydicobalt octacarbonyl (6.85 g). The mixture was stirred for three hours.The resulting tetrahydrofuran solution was decanted from the mercury andfiltered. The filter cake was rinsed down into the original filtratewith additional tetrahydrofuran. Triphenyltin chloride (15.4 g) wasadded to the filtrate and the mixture was stirred overnight. It was thenfiltered. The filtrate was evaporated to dryness and the residue wasstirred in tin tetrachloride (25 ml) for thirty minutes. This mixturewas filtered. The filtrate was concentrated on a rotary evaporator invacuum at ambient temperature until it was thick with a precipitate of ayellow crystalline solid. This was isolated by filtration, rinsed twicewith hexane and dried to obtain 6.24 g of (CO)₄ CoSnCl₃.Recrystallization from hexane gave 3.5 g recovery of this product in twocrops. Both the recrystallized and the unrecrystallized productsprepared in this fashion are suitable for use in the reactions describedherein.

"π-C₅ H₅ Fe(CO)₂ SnCl₃ "

One literature reference (Manning, Chem. Comm., 906 (1966) states thatthe reaction of π-C₅ H₅ Fe(CO)₂ I with excess SnCl₂.2H₂ O in methanolforms π-C₅ H₅ Fe(CO)₂ SnCl₂ I.CH₃ OH, while a more recent report by Maysand Pearson, J. Chem. Soc. (A), 136 (1969), says this is incorrect andthat the product, which is said to precipitate from the reactionmixture, is π-C₅ H₅ Fe(CO)₂ SnCl₃. It was found that this reaction givesa methanol-soluble species which has a chlorine:iodine ratio of 10:1.This product is suitable for use in the process of this invention as asource of the π-C₅ H₅ (CO)₂ Sn- moiety and is referred to herein inquotation marks, "π-C₅ H₅ Fe(CO)₂ SnCl₃ ", to reflect the uncertainty inits structure.

A mixture of commercially available π-C₅ H₅ -Fe(CO)₂ I (10 g), methanol(250 ml) and SnCl₂.2H₂ O (75 g) was refluxed for eight hours in anitrogen atmosphere and then let cool and stand for twelve hours. It wasfiltered to remove a small amount of dark solid and obtain an orangefiltrate. The slow addition of water to this filtrate caused theseparation of 10.8 g of "π-C₅ H₅ Fe(CO)₂ SnCl₃ " as a crystalline orangesolid.

    ______________________________________                                          Anal. Calcd for C.sub.5 H.sub.5 Fe(CO).sub.2 SnCl.sub.3 : C, 20.91;         H, 1.25; Cl, 26.46; Fe, 13.89; I, 0.0; Sn, 29.52                              Found:                                                                              C,     16.77;  H,   1.65; Cl, 23.76;                                                                              Fe,  11.02;                                      16.89        1.51      23.25      11.03                                I,     8.34;   Sn,  30.00                                                            8.26         30.32                                               ______________________________________                                    

p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnCl₃ was prepared as described by Parshall, J.Am. Chem. Soc., 88, 704 (1966).

π-C₅ H₅ W(CO)₃ SnCl₃ is described by Bonati and Wilkinson, J. Chem.Soc., 179 (1964). The material used in the present work was prepared bya different route:

a. A mixture of sodium cyclopentadienide (10.6 g), tetrahydrofuran (200ml) and tungsten hexacarbonyl (35.5 g) was refluxed overnight in anitrogen atmosphere and cooled. A solution of acetic acid (7.2 g) intetrahydrofuran (200 ml) was added and the mixture was stripped todryness. The residue was sublimed at 50° in vacuum to obtain 8.2 g ofπ-C₅ H₅ W(CO)₃ H. This was stirred for one hour in carbon tetrachlorideand filtered to obtain 7.1 g of π-C₅ H₅ W(CO)₃ Cl.

b. A mixture of anhydrous stannous chloride (29 g) and π-C₅ H₅ W(CO)₃ Cl(2.7 g) in diethylene glycol dimethyl ether (40 ml) was refluxed in anitrogen atmosphere for two hours and then allowed to cool and standovernight. It was then filtered in air. The major portion of thefiltrate was evaporated in a rotary evaporator under vacuum to leave aresidual oil. The oil was mixed with ethanol (25 ml), causing theseparation of crystalline orange π-C₅ H₅ W(CO)₃ SnCl₃ (1.2 g, dec 182°,lit mp 187° (Bonati and Wilkinson)).

Cl₃ SnFe(CO)₃ NO was prepared by the method of Casey and Manning, Chem.Comm., 674, (1970), with slight modification as reported here.

Tin tetrachloride (6 g) was added to Hg(Fe(CO)₃ NO)₂ (7.7 g) in 100 mlof toluene in a dry nitrogen atmosphere and stirred several hours. Themixture was filtered. Slight concentration of the filtrate causedprecipitation of 2.75 g of Cl₃ SnFe(CO)₃ NO as an orange red crystallinesolid which was rinsed three times with hexane and dried. An additional5.38 g was obtained by evaporating the filtrate to dryness. Both cropsof product had infrared spectra which agreed with that reported for Cl₃SnFe(CO)₃ NO by Casey and Manning.

Cl₃ SnFe(CO)₂ (P(C₆ H₅)₃)NO was prepared according to Casey and Manning,J. Chem. Soc., (A), 256 (1971), except that toluene was used as solventinstead of benzene.

Co₂ W₁₁ O₃₉.H₂ O⁷⁻

This anion was prepared according to Baker and McCutcheon, J. Am. Chem.Soc., 78, 4503 (1956). That paper described the isolation of an ammoniumsalt of [Co⁺² Co⁺³ W₁₂ O₄₂ ]⁻⁷ (anion II in that paper). Thischaracterization was erroneous and the formulation of the anion waslater (Baker et al, J. Am. Chem. Soc., 88, 2329 (1966)) corrected to [H₂Co⁺² O₆ Co⁺³ O₄ W₁₁ O₃ ]⁻⁷ (anion 4 in the latter paper) which isidentical to Co₂ W₁₁ O₃₉.H₂ O⁷⁻. The preparation given in the originalpaper was followed except that the product anion was isolated by atetramethylammonium salt.

Acetic acid (40 ml) was added to a solution of sodium tungstate (198 g)in 400 ml of water, bringing the pH to 7.1. A solution of cobaltousacetate tetrahydrate (24.9 g) in water (125 ml) plus five drops ofacetic acid was added. The solution was boiled for ten minutes andfiltered hot. The filtrate was heated to 80° and ammonium persulfate (15g) was added slowly. After the addition was complete, the mixture wasboiled for ten minutes and then cooled. The addition oftetramethylammonium chloride precipitated a dark brown solid which wasused as the starting material in Example 16.

π-C₅ H₅ Fe(CO)₂ GeCl₃ was prepared as described by Edmondson, Eisner,Newlands and Thompson, J. Organometal. Chem., 35, 119 (1972).

(C₆ H₅)₃ P(π-C₃ H₅)PdSnCl₃ was prepared according to Mason et al., Chem.Commun., 1655 (1968).

[(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnCl₃ was prepared by the method of Taylor,Young and Wilkinson, Inorg. Chem., 5, 20 (1966).

EXAMPLE 1 [(CH₃)₄ N]₅ (CO)₄ CoSnW₁₁ SiO₃₉

Cl₃ SnCo(CO)₄ (0.5 g, 1.3 mmoles) was added to a mixture of K₈ W₁₁SiO₃₉.10H₂ O (3.0 g, 0.95 mmoles) and water (10 ml). The mixture washeated to 60° briefly and filtered hot. Tetramethylammonium chloride inexcess was added to the filtrate, precipitating a light blue solid. Partof this (1.3 g) was recrystallized from a mixture of ethanol (20 ml) andwater (23 ml). The solid dissolved completely while the mixture was hot,forming a clear light yellow solution. This was allowed to cool but wasfiltered while still warm to separate 0.1 g of a yellow solid. Thefiltrate from this separation was allowed to cool to ambient temperatureand stand for two hours. Filtration then gave a light pink solid, A. Thefiltrate from the isolation of A was heated to 75° and diluted withethanol until it became cloudy. On cooling, this solution separatedadditional solid, B, which was identical with A by infrared analysis.The combined weight of A and B was 0.5 g. Solid A was analyzed and foundto contain [(CH₃)₄ N]₅ (CO)₄ CoSnW₁₁ SiO₃₉.12H₂ O.

    ______________________________________                                        Anal. Calcd for [(CH.sub.3).sub.4 N].sub.5 (CO).sub.4 CoSnW.sub.11            SiO.sub.39 . 12H.sub.2 O:                                                           C,     8.12;   H,   2.38; N,  1.97; Co,  1.66;                                O,     24.78;  Sn,  3.34                                                Found:                                                                              C,     7.36;   H,   1.97; N,  1.89; Co,  1.12;                                       7.36         2.00      1.82       1.10                                 O,     24.36;  Sn,  2.43                                                                          2.56                                                ______________________________________                                    

The presence of a significant amount of water was confirmed by infraredanalysis; the infrared spectrum also included bands at about 2110, 2050,2020 and 2000 cm⁻¹, consistent with the above formula.

EXAMPLE 2 [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂ H₁₁ (CO)₃ Co(SnW₁₁SiO₃₉)₂

A. A solution of Cl₃ SnCo(CO)₄ (4.0 g, 10.1 mmoles) in tetrahydrofuran(30 ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (20 g, 6.3mmoles) in water (150 ml) at 70°. The mixture was stirred at 70° for 15minutes, cooled to ambient temperature and filtered. The filtrate wasstripped to dryness; the residue was dissolved in water (40 ml). Excesstrimethylammonium chloride was added to precipitate a gray-green solidwhich was recrystallized from 285 ml of water which containedtrimethylammonium chloride (4 g), then from 80 ml of water and finallyfrom another 80 ml of water. The final product was dried at ambienttemperature in vacuum overnight to obtain 9.89 g of a hydrate of [(CH₃)₃NH]₁₁ (CO₃)-Co(SnW₁₁ SiO₃₉)₂ as a golden-yellow crystalline solid. Partof this was dried at 140° in vacuum overnight before analysis.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.11 (CO).sub.3 Co(SnW.sub.11       SiO.sub.39).sub.2 -                                                           . 4H.sub.2 O:                                                                       C,     6.69;  H, 1.86;                                                                             N,  2.38;                                                                             O, 21.04;                                        Co,    0.91;  Sn, 3.67;                                                                            Si. 0.87;                                                                             W, 62.57;                                        H.sub.2 O,                                                                           1.11                                                             Found:                                                                              C,     6.74;  H, 1.83;                                                                             N,  2.30;                                                                             O, 20.89;                                               6.85   1.90       2.34                                                                              21.16                                            Co,    0.86;  Sn, 3.47;                                                                            Si, 0.74;                                                                             W, 62.94;                                                                             H.sub.2 O,                                                                         1.27                                       0.87   3.45       0.74                                                                              62.62        1.24                          ______________________________________                                    

The infrared spectrum (mineral-oil mull) included a weak C.tbd.O band at2022 cm⁻¹ and stronger ones at 1959 and 1947 cm⁻¹, consistent with theabove formula. The ultraviolet spectrum in 0.01 N H₂ SO₄, determined ona sample prepared in similar fashion to the above, had λ_(max) 259 mμ (ε80,000) and λ_(max) 319 mμ (ε99,700).

B. A solution of [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂.4H₂ O (1.5087 g)in warm water (150 ml) was passed through an ion-exchange columncontaining 15 g of a strongly acidic ion-exchange resin [crosslinkedpoly(styrenesulfonic acid) type]. The column was rinsed until therinsings were no longer acidic. The original effluent and the rinsingswere combined to obtain an aqueous solution of H₁₁ (CO)₃ Co(SnW₁₁SiO₃₉)₂. The pH of this dilute solution was 2.05. Titration with 0.1 Nsodium hydroxide gave a titration curve typical of a strong acid; allprotons appeared to be of equivalent strength. The observed neutralequivalent was 612; the calculated neutral equivalent (based on theamount of [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂.4H₂ O used) is 588. Thetitration data suggest that nucleophilic decomposition of the anionstarts at about pH 7.

In a similar ion-exchange experiment with 1.5 g of the same salt, 100 mlof warm water and 20 ml of the same ion exchange resin, the acidiceffluent was evaporated to leave a green gum which redissolved in waterto give a yellow solution. The green gum was hydrated H₁₁ (CO)₃ Co(SnW₁₁SiO₃₉)₂.

EXAMPLE 3 K₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂

A solution of [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂ (11.5 g) in warmwater (400 ml) was passed through an ion-exchange column containing 35ml of the potassium salt of a crosslinked poly(styrenesulfonic acid)resin. The combined effluent and column rinsings were evaporated todryness and the residue was further dried at 140° in vacuum overnight toleave a hydrate of K₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂ as a dark-brown solid. Theinfrared spectrum of the solid was consistent with this formula.

EXAMPLE 4 Na₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂

A solution of [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂ (205 g) in warm (40°C.) water (5 liters) was passed through an ion-exchange columncontaining 1500 ml of a crosslinked poly(styrenesulfonic acid) resinwhich had largely been converted to a sodium salt beforehand withsolutions of sodium acetate and sodium hydroxide. The effluent andrinsings were combined and found to have a pH of 3. They were brought topH 6.4-6.5 with aqueous sodium hydroxide and evaporated to dryness toleave a solid hydrate of Na₁₁ (CO)₃ Co(SnW₁₁ SiO₃₉)₂. It was foundpreferable to use dilute (0.1 N to 0.2 N) sodium hydroxide solution forthe final neutralization rather than concentrated sodium hydroxidesolution because the latter can cause some decomposition of the aniondue to temporary local overbasification even with good stirring.

EXAMPLE 5 [(CH₃)₃ NH]₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂

A solution of lithium acetate (20 g) in water (30 ml) was adjusted to pH5.5 with acetic acid and added to a solution of tungstophosphoric acid(21 g, 6.9 mmoles) in water (70 ml) at 70° followed immediately by asolution of Cl₃ SnCo(CO)₄ (4.0 g, 10.1 mmoles) in tetrahydrofuran (20ml). An immediate red color formed; the temperature was maintained at70° for 5 minutes and the mixture was then filtered. The filtrate wasallowed to cool and was refiltered. Trimethylammonium chloride in excesswas added to the major portion of the filtrate to precipitate a solid,which was recrystallized three times from water, first from 100 ml. thenfrom 80 ml and finally from 50 ml, to obtain a golden-yellow crystallinesolid which was a hydrate of [(CH₃)₃ NH]₉ [(CO)₃ Co(SnW₁₁ PO₃₉)₂ ] (1.7g). This was dried at ambient temperature in vacuum.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.9 (CO).sub.3 Co(SnW.sub.11        PO.sub.39).sub.2 -                                                            . 12H.sub.2 O:                                                                      C,     5.55;  H,   1.77; N,  1.94; O,   22.80;                                Co,    0.91;  Sn,  3.66; W,  62.30;                                                                              H.sub.2 O,                                                                         3.32                            Found:                                                                              C,     6.38;  H,   1.60; N,  2.01; O,   21.00;                                       6.24        1.56      2.09       20.81                                 Co,    0.93;  Sn,  3.71; W,  64.02;                                                                              H.sub.2 O;                                                                         3.64                                         0.93        3.68      64.42      3.52                            ______________________________________                                    

The infrared spectrum included a weak C.tbd.O absorption band at 2031cm⁻¹ and stronger ones at 1971 and 1950 cm⁻¹, consistent with theassigned formulation.

If the foregoing process is essentially repeated, using tungstogermanicacid in place of tungstophosphoric acid, hydrated [(CH₃)₃ NH]₁₁ (CO)₃Co(SnW₁₁ GeO₃₉)₂ will be obtained.

EXAMPLE 6 K₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂

An aqueous solution of [(CH₃)₃ NH]₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂ was passedthrough an ion-exchange column containing an excess of the potassiumsalt of a crosslinked poly(styrenesulfonic acid) cation exchange resin.Evaporation of the effluent left 4.76 of a hydrate of K₉ (CO)₃ Co(SnW₁₁PO₃₉)₂. The ultraviolet spectrum in 0.01 N H₂ SO₄, determined on asample prepared in similar fashion to the above, had λ_(max) 258 mμ(k=13.6), 314 mμ (k=10.0).

EXAMPLE 7 [(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉

A solution of "π-C₅ H₅ Fe(CO)₂ SnCl₃ " (3.0 g, ca. 7.5 mmoles) inmethanol (30 ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (12.7 g,4.0 mmoles) in water (90 ml). The mixture was heated to 60° andmaintained at this temperature for five minutes. It was then cooled andfiltered. Excess trimethylammonium chloride was added to the filtrate toprecipitate an orange solid, which was recrystallized from water. Therecrystallized [(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉ (7.8 g) wasdried at 140° overnight before analysis.

    ______________________________________                                        Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.5 C.sub.5 H.sub.5 Fe(CO).sub.2      SnW.sub.11 SiO.sub.39 :                                                             C,      8.08;   H,  1.68;                                                                              N,   2.14;                                                                              Fe,  1.71;                                 O,      20.06;  Si. 0.86;                                                                              Sn,  3.63;                                                                              W,   61.83;                                H.sub.2 O,                                                                            0.0                                                             Found:                                                                              C,      8.31;   H,  1.73;                                                                              N,   2.08;                                                                              Fe,  1.57;                                         8.02        1.71      2.09      1.59                                  O,      20.80;  Si, 0.88;                                                                              Sn,  3.50;                                                                              W,   61.82                                         20.48       0.84      3.48      61.43                                 H.sub.2 O,                                                                            0.24                                                                          0.26                                                            ______________________________________                                    

The infrared spectrum (mineral-oil mull) displayed C.tbd.O stretchingabsorption frequencies at 2013 and 1961 cm⁻¹. The ultraviolet spectrum,determined in 0.01 N H₂ SO₄ had λ_(max) 260 mμ (ε 43,200), 418 (sh) (ε540). The proton nmr spectrum included resonances due to CH₃ -N and C₅H₅ protons in an integrated area ratio of 10.7:1, compared with acalculated ratio of 9:1.

If π-C₅ H₅ Ru(CO)₂ SnCl₃ is substituted for "π-C₅ H₅ Fe(CO)₂ SnCl₃ " inessentially the foregoing process, [(CH₃)₃ NH]₅ π-C₅ H₅ Ru(CO)₂ SnW₁₁SiO₃₉ will be obtained. If (dimethylglyoxime)₂ Co(NC₅ H₅)CoSnCl₃ is usedin place of "π-C₅ H₅ Fe(CO)₂ SnCl₃ ", the product will be [(CH₃)₃ NH]₅(dimethylglyoxime)₂ Co(NC₅ H₅)CoSnW₁₁ SiO₃₉.

EXAMPLE 8 K₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉

A solution of [(CH₃)₃ NH]π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉ (14.15 g) in warmwater (100 ml) was passed through an ion-exchange column containing 45ml of the potassium salt of a crosslinked poly(styrenesulfonic acid)cation-exchange resin. The column was rinsed down with water; therinsings and the original effluent were combined and evaporated todryness to leave 13.7 g of a hydrate of K₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ SiO₃₉.

EXAMPLE 9 [(CH₃)₄ N]₅ p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnW₁₁ SiO₃₉

A solution of p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnCl₃ (2.9 g, 3.9 mmoles) intetrahydrofuran (15 ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O(9.0 g, 2.8 mmoles) in water (75 ml) which had been heated to 50°. Themixture was stirred at 50°-54° for four minutes and filtered beforecooling. Tetramethylammonium chloride was added to a major portion ofthe filtrate to precipitate a white solid, which was separated byfiltration from a yellow liquid. The proton nmr spectrum of theprecipitate included resonances due to CH₃ -N, C₂ H₅ -P and p-FC₆ H₄ Ptprotons in intensity ratios of 63:28:3.7, compared to 60:30:4 calculatedfor the formulation [(CH₃)₄ N]₅ p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnW₁₁ SiO₃₉.This precipitate was recrystallized from 60 ml of 50% aqueous acetoneand dried at ambient temperature in vacuum overnight and then at 80° invacuum overnight to obtain a hexahydrate of the above salt.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.4 N].sub.5 FC.sub.6 H.sub.4 Pt[P(C.sub.2     H.sub.5).sub.3 ].sub.2 -                                                     SnW.sub.11 SiO.sub.39 . 6H.sub.2 O:                                                 C,    12.02;  H,   2.81;                                                                              N,  1.84; O,    18.95;                                Si,   0.74;   Sn,  3.12;                                                                              W,  53.24;                                                                              H.sub.2 O,                                                                          2.89.                           Found:                                                                              C,    12.13;  H,   2.54;                                                                              N,  1.99; O,    17.83;                                      12.12        2.68     1.90        17.97                                 Si,   0.87;   Sn,  3.10;                                                                              W,  53.76;                                                                              H.sub.2 O,                                                                          2.89                                        0.82         3.13     53.60       2.89                            ______________________________________                                    

If p-FC₆ H₄ Pt[P(C₂ H₅)₃ ]₂ SnCl₃ is replaced by C₆ H₅ Pt[P(C₂ H₅)₃ ]₂SnCl₃ and K₈ W₁₁ SiO₃₉.10H₂ O is replaced by K₈ W₁₁ GeO₃₉ hydrate inessentially the foregoing process, [(CH₃)₄ N]₅ C₆ H₅ Pt[P(C₂ H₅)₃ ]₂SnW₁₁ GeO₃₉ hydrate will be obtained.

EXAMPLE 10 [(CH₃)₃ NH]₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉

A solution of lithium acetate (15 g) in water (20 ml) was brought to pH7 with acetic acid and added to a solution of tungstophosphoric acid (12g, ca. 3.9 mmoles) in water (60 ml) at 60° followed rapidly by asolution of "π-C₅ H₅ Fe(CO)₂ SnCl₃ " (3.5 g, ca. 8.7 mmoles) in methanol(20 ml). The reaction temperature was maintained at 60° for fiveminutes. The mixture was then filtered twice. Trimethylammonium chloridewas added to the filtrate to precipitate a yellow solid, which wasrecrystallized from water (100 ml) and then digested briefly in boilingwater (50 ml). It was then dried in vacuum at room temperature to obtain4.1 g of the trihydrate of [(CH₃)₃ NH]₄ [π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉ ].

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.4 C.sub.5 H.sub.5 Fe(CO).sub.2     SnW.sub.11 PO.sub.39 -                                                       . 3H.sub.2 O:                                                                       C,     6.98;  H,   1.57,                                                                              N,  1.71; O,   21.54; Fe,                                    1.71;  Sn,  3.63;                                                                              W,  61.89;                                                                              H.sub.2 O;                                                                          1.65                            Found:                                                                              C,     7.05;  H,   1.51;                                                                              N,  1.74; O,   20.21;                                        7.06        1.48     1.67       21.26                                                                         20.48                                  Fe,    1.76;  Sn,  3.66;                                                                              W,  61.95;                                                                              H.sub.2 O,                                                                          1.89                                         1.80        3.65     62.16       1.92                            ______________________________________                                    

The proton nmr spectrum displays a CH₃ -N:C₅ H₅ proton ratio of 7.5:1compared to a calculated value of 7.2:1. The infrared spectrumdetermined in a mineral-oil mull includes C.tbd.O absorption bands at2021 and 1971 cm⁻¹. The ultraviolet spectrum, determined in 0.01 N H₂SO₄ on a sample prepared in a fashion similar to that described above,had a maximum at 260 mμ (ε 99,300) with a shoulder at 410 mμ (ε 621).

If "π-C₅ H₅ Fe(CO)₂ SnCl₃ " is replaced by π-C₅ H₅ Ni(CO)SnCl₃ andtungstophosphoric acid is replaced by tungstogermanic acid inessentially the foregoing process, [(CH₃)₃ NH]₅ π-C₅ H₅ Ni(CO)SnW₁₁GeO₃₉ or a hydrate thereof will be obtained.

EXAMPLE 11 K₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉

A solution of [(CH₃)₃ NH]₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉ (18 g) in hotwater (250 ml) was passed through an ion-exchange column containing 55ml of the potassium salt of a crosslinked poly(styrenesulfonic acid)cation-exchange resin. The column was rinsed down with water. Thecombined original effluent and rinsings were evaporated to dryness toleave 17.4 g of a solid hydrate of K₄ π-C₅ H₅ Fe(CO)₂ SnW₁₁ PO₃₉.

EXAMPLE 12 [(CH₃)₄ N]₅ π-C₅ H₅ W(CO)₃ SnW₁₁ SiO₃₉

A solution of π-C₅ H₅ W(CO)₃ SnCl₃ (1.1 g, 2.0 mmoles) intetrahydrofuran (15 ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O(5.0 g, 1.6 mmoles) in water (50 ml) which had been heated to 70°. Themixture was stirred at 70° for five minutes and then filtered. Theaddition of excess tetramethylammonium chloride to the filtrate causedprecipitation of a gray solid. This was dissolved in boiling water (30ml) which was allowed to cool to ambient temperature. A mixture of grayand lighter-colored solids was obtained. This mixture, still in the 30ml of water, was reheated to redissolve the solids. The solution wasallowed to cool until the gray solid had crystallized and was thenfiltered. The filtrate was reheated and filtered again while hot toobtain a small amount of an insoluble solid and an orange filtrate. Thefiltrate was allowed to cool; a cream colored, almost light yellow solidseparated. This was dried at ambient temperature in vacuum and found tocomprise 2.5 g of [(CH₃)₄ N]₅ π-C₅ H₅ W(CO)₃ SnW₁₁ SiO₃₉.6H₂ O.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.4 N].sub.5 C.sub.5 H.sub.5 W(CO).sub.3      SnW.sub.11 SiO.sub.39 -                                                       . 6H.sub.2 O:                                                                       C,    9.32;  H,   2.15;                                                                              N,   1.94; O,    21.30;                                Si.   0.78;  Sn,  3.29;                                                                              W,   61.20;                                                                              H.sub.2 O,                                                                          3.00.                           Found:                                                                              C,    9.99;  H,   2.10;                                                                              N,   2.12; O,    20.48;                                      9.82        2.06      2.0         20.75                                 Si,   0.89;  Sn,  3.27;                                                                              W,   61.10;                                                                              H.sub.2 O,                                                                          3.33                                        0.87        3.31      61.60       3.37                            ______________________________________                                    

The proton nmr spectrum displayed a CH₃ N:C₅ H₅ proton ratio of 13.5:1compared to a calculated ratio of 12:1. The infrared spectrum,determined in a mineral-oil mull, included a C.tbd.O absorption based at2015 cm⁻¹ and one at 1911 cm⁻¹ with a shoulder at about 1945 cm⁻¹.

If π-C₅ H₅ W(CO)₃ SnCl₃ is replaced by π-C₅ H₅ Mo(CO)₂ P(C₆ H₅)₃ SnI₃ inessentially the foregoing process, a hydrate of [(CH₃)₄ N]₅ π-C₅ H₅Mo(CO)₂ P(C₆ H₅)₃ SnW₁₁ SiO₃₉ will be obtained.

EXAMPLE 13 [(CH₃)₃ NH]₁₁ (CO)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂

Cl₃ SnFe(CO)₃ NO (2.75 g, 7.0 mmoles) was added to methanol (10 ml).There was immediate gas evolution. After this had subsided, the nowdark-red solution was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (9.0 g,2.84 mmoles) in water (60 ml) at 60°. The mixture was stirred for fiveminutes at 60° and then filtered at this temperature. Trimethylammoniumchloride was added to the major portion of the reaction mixture toprecipitate a solid which was recrystallized two times, 60 ml of waterbeing used each time. The hot solution was filtered through diatomaceousearth during the second crystallization. A crystalline yellow solid (3.6g) was obtained which was dried at room temperature in vacuum to obtain[(CH₃)₃ NH]₁₁ (CO)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂.7H₂ O.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.11 (CO).sub.2 Fe(NO)-             (SnW.sub.11 SiO.sub.39).sub.2 . 7H.sub.2 O:                                         C,     6.45;  H,  1.92;                                                                              N,   2.58;                                                                              O,  21.60,                                                                              Fe,                                       0.88;  Si, 0.86;                                                                              Sn,  3.64;                                                                              W,  62.08;                                                                              H.sub.2 O,                                1.93.                                                            Found:                                                                              C,     6.45;  H,  1.70;                                                                              N,   2.56;                                                                              O,  20.10;                                          6.46       1.62      2.59     20.08                                    Fe,    0.88;  Si, 0.90;                                                                              Sn,  3.59,                                                                              W,  62.29                                           0.86       0.87      3.50     62.04                                    H.sub.2 O,                                                                           1.86                                                                          1.92                                                             ______________________________________                                    

The infrared spectrum, determined in a mineral-oil mull, displayedC.tbd.O stretching absorption bands at 1980 and 1930 cm⁻¹ and anabsorption for the NO group at 1730 cm⁻¹. The ultraviolet spectrum,determined in 0.01 N H₂ SO₄ on a sample prepared in a similar fashion,had a maximum at 260 mμ (ε 79,300).

If K₈ W₁₁ SiO₃₉.10H₂ O is replaced by K₇ W₁₁ PO₃₉ in essentially theforegoing process, the product obtained will be [(CH₃)₃ NH]₉ (OC)₂Fe(NO)[SnW₁₁ PO₃₉ ]₂ hydrate.

EXAMPLE 14 K₁₁ (CO)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂

A solution of [(CH₃)₃ NH]₁₁ (CO)₂ Fe(NO)SnW₁₁ SiO₃₉)₂ (20.9 g) in water(1 liter) was passed through an ion-exchange column containing 90 ml ofthe potassium salt of a crosslinked poly(styrenesulfonic acid)cation-exchange resin. The effluent was evaporated to dryness to leave asolid hydrate of K₁₁ (OC)₂ Fe(NO)(SnW₁₁ SiO₃₉)₂.

EXAMPLE 15 K₈ (CO)₃ Co(SnO₃)SnW₁₁ PO₃₉

A. Potassium cyanide was added to an aqueous solution of K₉ (CO)₃Co(SnW₁₁ PO₃₉)₂ at room temperature. A yellow solid precipitatedimmediately. The infrared spectrum of this solid, later shown to be ahydrate of K₈ (CO)₃ Co(SnO₃)SnW₁₁ PO₃₉ (see below), had absorption bandsfor C.tbd.O resembling those in the starting heteropolyanion, K₉ (CO)₃Co(SnW₁₁ PO₃₉)₂, but was much more opaque at 900-700 cm⁻¹.

B. Potassium cyanide (1.0 g) was added to a solution of K₉ (CO)₃Co(SnW₁₁ PO₃₉)₂ (2.0 g) in water (10 ml). The yellow solid whichseparated was removed by filtration and washed with water six times. Itwas dried at 80° in vacuum to obtain 0.7 g of K₈ (OC)₃ Co(SnO₃)SnW₁₁PO₃₉.12H₂ O, which can also be formulated as K₅ (CO)₃ Co[Sn(OK)₃ ]SnW₁₁PO₃₉.12H₂ O.

    __________________________________________________________________________    Anal. Calcd for K.sub.8 (CO).sub.3 Co( SnO.sub.3)SnW.sub.SnW.sub.11           PO.sub.39                                                                         C, 0.99;                                                                            H, 0.67;                                                                            N, 0.00;                                                                             C,  25.09;                                                                            Co,                                                                              1.62;                                           K, 8.60;                                                                            Sn,                                                                              6.53;                                                                            W, 55.64;                                                                            H.sub.2 O,                                                                        5.94                                               Found:                                                                            C, 0.78;                                                                            H, 0.46;                                                                            N, 0.1;                                                                              O,  23.90;                                                    0.75  0.20  0.1                                                            Co,                                                                              1.57;                                                                            K, 8.49;                                                                            Sn,                                                                              6.24;                                                                             W,  55.72;                                                    1.57  8.40  6.14    55.28                                                  H.sub.2 O,                                                                       5.73                                                                          5.76                                                                   __________________________________________________________________________

EXAMPLE 16 [(CH₃)₄ N]₇ π-C₅ H₅ Fe(CO)₂ SnW₁₁ CoO₃₉

A solution of lithium acetate (10 g) in water (20 ml) was brought to pH6.5 with acetic acid, heated to 50° and then added to a solution of thedark-brown solid which was prepared as described earlier (12.8 g) inwater (30 ml) which had been heated to 50°. This was followedimmediately by the addition of a solution of "π-C₅ H₅ Fe(CO)₂ SnCl₃ " (2, ca. 5 mmoles) in methanol (15 ml) which had been heated to 50°. Themixture was then warmed to 60° and stirred at this temperature forfifteen minutes. It was filtered while still hot; the filtrate wasrefiltered after it had cooled to obtain a dark blue filtrate to whichwas added tetramethylammonium chloride. A small amount of dark bluesolid separated and was removed by filtration. The filtrate wasconcentrated in stages with precipitated solids being removed betweenstages. This was continued until the infrared spectrum of the solidisolated included substantial carbonyl absorption bands (at ca 2010 and1960 cm⁻¹). This fraction (A) was a crystalline dark green solid (2.2g). The filtrate from the isolation of this solid was concentratedfurther and a portion of the concentrate was diluted with methanol toprecipitate 0.6 g of a green solid (B). This had an infrared spectrumalmost identical with that of fraction A except that the relativeintensity of the carbonyl absorption bands in the spectrum of B wasslightly greater than in the spectrum of A, implying that B was slightlymore pure than A.

    ______________________________________                                        Anal. Calcd for [(CH.sub.3).sub.4 N].sub.7 C.sub.5 H.sub.5 Fe(CO).sub.2       SnW.sub.11 CoO.sub.39 :                                                             C,     11.94;  H,   2.55; N,   2.79;                                                                              Co,  1.67;                                Fe,    1.59;   Sn,  3.37.                                               Found:               C,   11.51;                                                                              H,   3.26;                                                                              N,   2.42;                          (`B`):                    1.48       3.00      2.37                                 Co,    1.79;   Fe,  1.17; Sn,  2.80                                                  1.78         1.16       2.74                                     ______________________________________                                    

If (n-C₄ H₉)₃ PCo(CO)₃ SnCl₃ is used in place of "π-C₅ H₅ Fe(CO)₂ SnCl₃", the product will be [(CH₃)₄ N]₇ (n-C₄ H₉)₃ PCo(CO)₃ SnW₁₁ CoO₃₉.

EXAMPLE 17 [(CH₃)₄ N]₅ (CO)₂ Fe(NO)[P(C₆ H₅)₃ ]SnW₁₁ SiO₃₉

A solution of K₈ W₁₁ SiO₃₉.10H₂ O (2.3 g, 7.3 mmoles) in water (150 ml)was heated to 50°. A solution of (CO)₂ Fe(NO)[P(C₆ H₅)₃ ]SnCl₃ (5.7 g,7.3 mmoles) in tetrahydrofuran (50 ml) was added and the reactionmixture was stirred and heated at 50°-60° for thirty minutes. The majorportion of the reaction mixture was filtered; the addition oftetramethylammonium chloride to the filtrate precipitated a yellowsolid, which was recrystallized from 900 ml of water. Therecrystallization filtrate was allowed to cool and the liquid portion,which contained a finely divided suspended yellow solid, was decantedfrom the bulk of the solid, which had settled to the bottom of thevessel. The latter solid was then isolated and dried at ambienttemperature in vacuum overnight to obtain 7.2 g of [(CH₃)₄ N]₅ (CO)₂Fe(NO)[P(C₆ H₅)₃ ]SnW₁₁ SiO₃₉.5H₂ O.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.4 N].sub.5 (CO).sub.2 Fe(NO)[P(C.sub.6      H.sub.5).sub.3 ]-                                                             SnW.sub.11 SiO.sub.39 . 5H.sub.2 O:                                                 C,     13.13;  H,   2.34;                                                                              N,  2.30; O,  20.55; Fe,                             1.53;  Sn,     3.24;                                                                              W,   55.29;                                                                            Si,    0.77;                                     H.sub.2 O,                                                                           2.46                                                             Found:                                                                              C,     11.13;  H,   2.02;                                                                              N,  1.94; C,  20.01;                                        11.27        2.01     1.95      19.94                                  Fe,    1.36;   Sn,  2.56;                                                                              W, 56.83;                                                                         Si,    0.83;                                            1.34         2.53     56.25      0.77                                  H.sub.2 O,                                                                           2.66                                                                          2.65                                                             ______________________________________                                    

The proton nmr spectrum displayed a methyl:aryl ratio of 4.4:1, comparedto a calculated ratio of 4:1. The infrared spectrum, determined in amineral-oil mull, included C.tbd.O absorption bands at about 2040 and1960 cm⁻¹ and an NO absorption band at about 1755 cm⁻¹.

If (C₆ H₅ O)₃ PFe(CO)₂ (NO)SnCl₃ is used in place of (OC)₂ Fe(NO)P(C₆H₅)₃ SnCl₃ and K₈ W₁₁ GeO₃₉ hydrate is used in place of K₈ W₁₁SiO₃₉.10H₂ O in essentially the preceding process, the product will be[(CH₃)₄ N]₅ (C₆ H₅ O)₃ PFe(CO)₂ (NO)SnW₁₁ GeO₃₉.

EXAMPLE 18 [(CH₃)₃ NH]₄ (π-C₅ H₅ Fe(CO)₂ Ge)₂ W₁₁ SiO₄₀

A solution of π-C₅ H₅ Fe(CO)₂ GeCl₃ (4.3 g, 12.1 mmoles) in methanol (30ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (25 g, 7.89 mmoles)in water (180 ml) at 60°. The mixture was stirred at 60° for ten minutesto obtain a clear orange solution. This was filtered and excesstrimethylammonium chloride was added to the filtrate, precipitating ayellow solid. This was isolated by filtration, washed with water anddried overnight at ambient temperature in vacuum. The yield at thispoint was 26.23 g. Five grams of this was recrystallized from 450 ml ofwater. The yellow solid recovered from the recrystallization was driedat ambient temperature overnight to obtain 1.6 g of [(CH₃)₃ NH]₄ (π-C₅H₅ Fe(CO)₂ Ge)₂ W₁₁ SiO₄₀. The infrared spectrum of the crude productwas nearly identical with that of the recrystallized solid and includedstrong C.tbd.O absorption bands at ca. 1990 and 2040 cm⁻¹.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.4 (C.sub.5 H.sub.5 Fe(CO).sub.    2 Ge).sub.2 -                                                                 W.sub.11 SiO.sub.40 :                                                               C,    9.10;   H,   1.46;                                                                              N,    1.63;                                                                              O,   20.52;                                K,    0.0;    Fe,  3.24;                                                                              Ge,   4.23;                                                                              Si,  0.82;                                 W,    58.96;  H.sub.2 O,                                                                         0.0.                                                 Found:                                                                              C,    9.03;   H,   1.53;                                                                              N,    1.61;                                                                              O,   20.51;                                      9.06         1.53       1.61      20.44                                 K,    0.0;    Fe,  3.30;                                                                              Ge,   3.77;                                                                              Si,  1.03;                                               3.30      3.84       1.02                                       W,    57.53;  H.sub.2 O,                                                                         0.16                                                             57.25        0.25                                                 ______________________________________                                    

The proton nmr spectrum had a CH₃ -N:C₅ H₅ proton ratio of 3.5:1compared to a calculated ratio of 3.6:1.

EXAMPLE 19 [(CH₃)₃ NH]₃ [π-C₅ H₅ Fe(CO)₂ Ge]₂ W₁₁ PO₄₀

A solution of lithium acetate (15 g) in water (20 ml) was brought to pH7 with acetic acid and then added to a solution of tungstophosphoricacid (11 g, 3.6 mmoles) in water (60 ml) which had been heated to 60°. Asolution of π-C₅ H₅ Fe(CO)₂ GeCl₃ (2.74 g, 7.7 mmoles) in methanol (15ml) was added and the mixture was heated to 60° briefly. It was filteredto obtain a small amount of yellow solid and a yellow filtrate. Analiquot of this filtrate was mixed with trimethylammonium chloride toprecipitate an almost white solid. The infrared spectrum of this solidhad very weak carbonyl (C.tbd.O) absorption bands. The yellow solid fromthe first filtration was dissolved in methanol (15 ml) and added to theremainder of the original yellow filtrate. The resulting solution washeated to boiling (90°) briefly. An aliquot of this solution was mixedwith tetramethylammonium chloride to precipitate a white solid which wasnot investigated further. The remainder of the yellow filtrate wasbrought to pH 3.8 by the dropwise addition of concentrated hydrochloricacid. The color became a much deeper yellow orange during this addition.Excess trimethylammonium chloride was added, precipitating abright-yellow solid. The infrared spectrum of this solid, determined ina mineral-oil mull, had strong C.tbd.O absorption bands at ca. 2050 and2000 cm⁻¹. The proton nmr spectrum had a CH₃ -N:C₅ H₅ proton ratio of2.67:1 compared to a ratio of 2.7:1 calculated for [(CH₃)₃ NH]₃ (π-C₅ H₅Fe(CO)₂ Ge)₂ W₁₁ PO₄₀. The 5.7 g of this solid that was obtained wasrecrystallized from 550 ml of water to obtain 4.9 g of recrystallizedyellow [(CH₃)₃ NH]₃ (π-C₅ H₅ Fe(CO)₂ Ge)₂ W₁₁ PO₄₀.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.3 [C.sub.5 H.sub.5 Fe(CO).sub.    2 Ge].sub.2 -                                                                 W.sub.11 PO.sub.40 :                                                                C,     8.20;  H,   1.05;                                                                              N,    1.25; O,  20.90;                                Fe,    3.32;  Ge,  4.31;                                                                    3.95                                                      Found:                                                                              C,     8.27;  H,   1.18;                                                                              N,    1.25; O,  20.36;                                       8.24        1.17       1.20      20.21                                                                         19.66                                 Fe,    3.42;  Ge,  3,.87;                                                                             H.sub.2 O,                                                                          0.46                                                   3.50                   0.46                                      ______________________________________                                    

If the above process is repeated in its essentials, but replacing π-C₅H₅ Fe(CO)₂ GeCl₃ with the species listed in column A, and thetungstophosphoric acid with the species in column B, the correspondingproduct in column C will be obtained.

    ______________________________________                                        A            B           C                                                    ______________________________________                                        (C.sub.6 H.sub.5).sub.3 PCo(CO).sub.3 -                                                    Unchanged   [(CH.sub.3).sub.3 NH].sub.3 - -GeCl.sub.3  [(C.su                             b.6 H.sub.5).sub.3 PCo(CO).sub.3 -                                            Ge].sub.2 W.sub.11 PO.sub.40                         (C.sub.6 H.sub.5).sub.3 AsCo-                                                              Tungstosilic                                                                              [(CH.sub.3).sub.3 NH].sub.4 -                        (CO).sub.3 GeCl.sub.3                                                                      Acid        [(C.sub.6 H.sub. 5).sub.3 AsCo(CO).sub.3 -                                    Ge].sub.2 W.sub.11 SiO.sub.40                        π-C.sub.5 H.sub.5 Ni[P(C.sub.2 -                                                        Tungstogermanic                                                                           [(CH.sub.3).sub.3 NH].sub.4 -                        H.sub.5).sub.3 GeCl.sub.3                                                                  Acid        [π-C.sub.5 H.sub.5 (C.sub.2 H.sub.5).sub.3 -                               PNiGe].sub.2 W.sub.11 GeO.sub.40                     ______________________________________                                    

EXAMPLE 20 [(CH₃)₃ S]₄ (H)π-C₅ H₅ Fe(CO)₂ SnMo₁₁ SiO₃₉

A solution of potassium acetate (30 g) in water (40 ml) was adjusted topH 5 with acetic acid and added to a solution of Na₄ Mo₁₂ SiO₄₀ (15 g,ca. 7.5 mmole) in water (100 ml). The resulting mixture was heated to50° and a solution of "π-C₅ H₅ Fe(CO)₂ SnCl₃ " (5.02 g, ca. 12.5 mmoles)in methanol (40 ml) was added. The reaction mixture was then stirred at50° for five minutes and filtered. Trimethylsulfonium iodide (excess)was added to the dark-yellow-brown filtrate to precipitate a brownsolid. This was stirred in boiling water (100 ml) and the solution wasfiltered hot; the filtrate was refiltered after it had cooled slightlyto remove the initial solid that separated. It was then allowed to cooland stand overnight at room temperature. Filtration gave a yellow-brownsolid which was dried at ambient temperature in vacuum to obtain 4.5 gof [(CH₃)₃ S]₄ (H)π -C₅ H₅ Fe(CO)₂ SnMo₁₁ SiO₃₉.4H₂ O.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 S].sub.4 (H)C.sub.5 H.sub.5 Fe(CO).sub    .2 SnMo.sub.11 -                                                              SiO.sub.39 . 4H.sub.2 O:                                                            C,     9.56;   H,  2.11; S,   5.38;                                                                              O,   30.19;                                Fe,    2.33;   Si, 1.18; Sn,  4.98;                                                                              Mo,  44.26;                                H.sub.2 O,                                                                           3.02                                                             Found:                                                                              C,     9.77;   H,  1.83; S,   5.99;                                                                              O,   28.31;                                       9.81        1.81       5.89      28.59                                        9.74        2.07                                                              9.90        2.07                                                       Fe,    2,24;   Si, 1.43; Sn,  4.88;                                                                              Mo,  45.43;                                       2.30        1.37       4.86      45.37                                 H.sub.2 O,                                                                           3.47                                                                          3.29                                                             ______________________________________                                    

The proton nmr spectrum had a CH₃ -S:C₅ H₅ proton ratio of 8.25:1compared to 7.2:1 calculated. The infrared spectrum, determined in amineral oil mull, included C.tbd.O absorption bands at ca. 2040 and 1980cm⁻¹. An aqueous slurry of the compound had a pH of 4.0, consistent withits formulation as an acid salt.

If the foregoing process is repeated in its essentials but replacing"π-C₅ H₅ Fe(CO)₂ SnCl₃ " with the reagents listed in Column A, thecorresponding products in Column B will be obtained.

    ______________________________________                                        A                 B                                                           ______________________________________                                        π-C.sub.5 H.sub.5 Mo(CO).sub.2 P(OCH.sub.3).sub.3 SnCl.sub.3                                 [(CH.sub.3).sub.3 S].sub.4 (H)π-C.sub.5 H.sub.5 Mo-                        (CO).sub.2 P(OCH.sub.3).sub.3 SnMo.sub.11 SiO.sub.39        π-C.sub.5 H.sub.5 Ru(CO).sub.2 SnCl.sub.3                                                    [(CH.sub.3).sub.3 S].sub.4 (H)π-C.sub.5 H.sub.5 Ru-                        (CO).sub.2 SnMo.sub.11 SiO.sub.39                           [(C.sub.6 H.sub.5).sub.2 PCH.sub.2 CH.sub.2 P-                                                  [(CH.sub.3).sub.3 S].sub.4 (H)[(C.sub.6 H.sub.5).sub.2                        PCH.sub.2 -                                                 (C.sub.6 H.sub.5).sub.2 ].sub.2 Re(CO)SnCl.sub.3                                                CH.sub.2 P(C.sub.6 H.sub.5).sub.2 ].sub.2 Re(CO)-                             SnMo.sub.11 SiO.sub.39                                      ______________________________________                                    

EXAMPLE 21 [(CH₃)₄ N]₁₀ SnW₁₁ SiO₃₉ Co(CO)₃ SnW₁₁ PO₃₉

A mixture of K₅ (CO)₃ Co[Sn(OK)₃ ]SnW₁₁ PO₃₉ (0.7 g) (Example 18 B) andwater (30 ml) was brought to pH 4.9 by the addition of three drops ofglacial acetic acid. K₈ W₁₁ SiO₃₉.10H₂ O (0.64 g) was added withstirring. The mixture was heated to 60° to obtain a clear orangesolution, pH 6.12, which was cooled to ambient temperatue. The additionof tetramethylammonium chloride precipitated an orange solid. This wasrecrystallized from a small amount of dilute aqueous tetramethylammoniumchloride to obtain 0.81 g of [(CH₃)₄ N]₁₀ SnW₁₁ SiO₃₉ Co(CO)₃ SnW₁₁PO₃₉.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.4 N].sub.10 SnW.sub.11 SiO.sub.39           Co(CO).sub.3 -                                                                SnW.sub.11 PO.sub.39 :                                                              C,     7.98;  H,   1.87;                                                                              N,   2.16; Co,   0.91;                                Si,    0.43;  Sn,  3.67                                                 Found:                                                                              C,     8.12;  H,   1.97;                                                                              N,   2.21; Co,   1.06;                                       8.32        2.00      2.19        1.15                                 Si,    0.70;  Sn,  4.54                                                              0.69        4.57                                                 ______________________________________                                    

The infrared spectrum includes absorption bands for C.tbd.O, P-O, andSi-O moieties.

If this process is repeated, but using molybdosilicic acid (whichdegrades to Mo₁₁ SiO₃₉ ⁸⁻ at the pH specified) in place of K₈ W₁₁SiO₃₉.10H₂ O, the product will be [(CH₃)₄ N]₁₀ SnW₁₁ SiO₃₉ Co(CO)₃SnMo₁₁ SiO₃₉.

EXAMPLE 22 [(CH₃)₃ NH]₄ π-C₅ H₅ Co(CO)(GeOH)₂ W₁₁ SiO₃₉

A solution of π-C₅ H₅ Co(CO)(GeCl₃)₂ (1.02 g) in warm methanol (10 ml)was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (3.2 g) in water (20 ml)at 60°. The mixture was stirred for ten minutes at 50°-60° and thenfiltered. The addition of trimethylammonium chloride to the yellowfiltrate precipitated a yellow solid, which was recrystallized fromwater to obtain 1.1 g of [(CH₃)₃ NH]₄ π-C₅ H₅ Co(CO)(GeOH)₂ W₁₁SiO₃₉.3H₂ O.

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.4 C.sub.5 H.sub.5 Co(CO)(GeOH)    .sub.2 -                                                                      W.sub.11 SiO.sub.39 . 3H.sub.2 O:                                                   C,     6.55;  H,   1.62;                                                                              N,    1.70; O,  21.82;                                Co,    1.79;  Ge,  4.40;                                                                              H.sub.2 O,                                                                          1.64                                      Found:                                                                              C,     6.76;  H,   1.42;                                                                              N,    1.68; O,  19.82;                                       6.78        1.51       1.68      20.08                                 Co,    2.16;  Ge,  5,20;                                                                              H.sub.2 O,                                                                          1.82                                                   2.16        5.16       1.67                                      ______________________________________                                    

The infrared spectrum displays C.tbd.O stretching absorption at about2080 cm⁻¹ ; the proton nmr spectrum shows the presence of methyl andcyclopentadienyl protons in a 7.1:1 ratio (calc'd 7.2:1).

If the foregoing process is repeated but replacing π-C₅ H₅ Co(CO)[GeCl₃]₂ with the reagent in column A and K₈ W₁₁ SiO₁₉ with the reagent incolumn B, the product in column C will be obtained.

    ______________________________________                                        A            B            C                                                   ______________________________________                                        π-C.sub.5 H.sub.5 Co(CO)-                                                               K.sub.8 W.sub.11 GeO.sub.39                                                                [(CH.sub.3).sub.3 NH].sub.4 πC.sub.5 H.sub.5                               -                                                   (GeBr.sub.3).sub.2        Co(CO)(GeOH).sub.2 -                                                          W.sub.11 GeO.sub.39                                 (C.sub.6 H.sub.5 NC).sub.2 Pd-                                                             K.sub.7 W.sub.11 PO.sub.39                                                                 [(CH.sub.3).sub.3 NH].sub.3 -                       (GeCl.sub.3).sub.2        (C.sub.6 H.sub.5 NC).sub.2 Pd-                                                (GeOH).sub.2 W.sub.11 PO.sub.39                     ______________________________________                                    

EXAMPLE 23 [(CH₃)₃ NH]₄ (C₇ H₈)₂ RhSnW₁₁ PO₃₉

A solution of lithium acetate (15 g) in water (80 ml) was adjusted to pH6 with acetic acid. Tungstophosphoric acid (11 g) was added; the pH wasthen 5.0. Solid (C₇ H₈)₂ RhSnCl₃ (1.8 g; C₇ H₈ =norbornadiene) was addedand the mixture was stirred for several minutes at ambient temperatureand then filtered. The addition of trimethylammonium chloride to thedark-red filtrate precipitated a rust-colored solid. This wasrecrystallized from water to obtain 8.9 g of [(CH₃)₃ NH]₄ (C₇ H₈)₂RhSnW₁₁ PO₃₉.H₂ O (after drying in vacuum at ambient temperature).

    ______________________________________                                          Anal. Calcd for [(CH.sub.3).sub.3 NH].sub.4 (C.sub.7 H.sub.8).sub.2         RhSnW.sub.11 -                                                                PO.sub.39 . H.sub.2 O:                                                              C,     9.34;  H,   1.75;                                                                              N,    1.68;                                                                              O,   19.15;                                Rh,    3.08;  Sn,  3.55;                                                                              H.sub.2 O,                                                                          0.54;                                     Found:                                                                              C,     9,38;  H,   1.73;                                                                              N,    1.57;                                                                              O,   18.83                                        9.36        1.68       1.56      19.11                                 Rh,    2.75;  Sn,  3.55;                                                                              H.sub.2 O,                                                                          0.82                                                   2.79        3.45       0.84                                      ______________________________________                                    

The proton nmr spectrum was consistent with the above formula.

If the foregoing process is repeated, replacing the (C₇ H₈)₂ RhSnCl₃with the reagent in column A and the tungstophosphoric acid with thereagent in column B, the product in column C will be obtained:

    ______________________________________                                        A           B             C                                                   ______________________________________                                        (C.sub.7 H.sub.8).sub.2 IrSnCl.sub.3                                                      Tungstosilicic                                                                              [(CH.sub.3).sub.3 NH].sub.5 -                                   Acid          (C.sub.7 H.sub.8).sub.2 IrSn-                                                 W.sub.11 SiO.sub.39                                 (Ph.sub.3 As).sub.2 (C.sub.8 H.sub.12)-                                                   Tungstogermanic                                                                             [(CH.sub.3).sub.3 NH].sub.5 (Ph.sub.3 -             IrSnCl.sub.3                                                                              Acid          As).sub.2 C.sub.8 H.sub.12 IrSn-                                              W.sub.11 GeO.sub.39                                 C.sub.7 H.sub.8 Co(CO).sub.2 -                                                            Tungstosilicic                                                                              [(CH.sub.3).sub.3 NH].sub.5 -                       SnCl.sub.3  Acid          C.sub.7 H.sub.8 Co(CO).sub.2 Sn-                                              W.sub.11 SiO.sub.39                                 ______________________________________                                    

EXAMPLE 24 [(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ GeO₃₉

12-Tungstogermanic acid (12 g, Polysciences, Inc.) was added to asolution of lithium acetate (15 g) in water (60 ml) after the solutionhad been brought to pH 5.5 by the addition of acetic acid. The resultingmixture (pH 5.2) was heated to 50° and a warm solution of "π-C₅ H₅Fe(CO)₂ SnCl₃ " (3 g) in warm methanol (35 ml) was added. The reactionmixture was then heated at 60°-70° for five minutes and filtered. Theaddition of trimethylammonium chloride precipitated a yellow-brown solidwhich was recrystallized two times from water. The product from thesecond recrystallization was collected in two fractions. The firstfraction was obtained by filtration after the hot recrystallization hadbeen allowed to cool normally for two hours. The filtrate from thisseparation was reheated to boiling, allowed to cool for three hours andthen filtered to obtain a second fraction, which consisted of 0.55 g ofyellow [(CH₃)₃ NH]₅ π-C₅ H₅ Fe(CO)₂ SnW₁₁ GeO₃₉. This was dried atambient temperature in vacuum overnight before analysis.

    ______________________________________                                          Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.5 C.sub.5 H.sub.5 Fe(CO).sub.    2 Sn-                                                                         W.sub.11 GeO.sub.39 :                                                               C,     7.97;  H,    1.67;                                                                              N,   2.11; Fe,  1.68;                                Ge,    2.19;  Sn,   3.58                                                Found:                                                                              C,     7.92;  H,    1.57;                                                                              N,   1.90; Fe,  1.75;                                       7.97         1.57      1.93       1.74                                 Ge,    2.02;  Sn,   3.56                                                             1.98         3.56                                                ______________________________________                                    

The proton nmr spectrum exhibited C₅ H₅ and CH₃ resonances in anintegral ratio of 1:9.1 (Calc'd 1:9).

EXAMPLE 25 {[(CH₃)₃ NH]₅ (CO)₃ CoGe₂ W₁₁ SiO₄₀ }_(y)

A solution of (CO)₄ CoGeCl₃ (7.0 g, 20 mmoles) in tetrahydrofuran (30ml) was added, in a nitrogen atmosphere, to a solution of K₈ W₁₁SiO₃₉.10H₂ O (20 g, 6.3 mmoles) at 60°-65°. The reaction mixture washeated 15 minutes in this temperature range and then filtered throughsintered glass and then through pre-wet filter paper. Excesstrimethylammonium chloride was added to the filtrate. Filtration thengave a dark-brown solid plus a blue filtrate. The solid was extractedwith 50 ml of boiling water in air; part of the solid (A) did notdissolve. The dark-blue extract was filtered hot, the filtrate wasallowed to cool to 40°-45° and filtered at this temperature to obtain ayellow solid (B), which was rinsed three times with small portions ofwater. The infrared spectrum of B confirmed that it had an (CO)₃ Corather than an (CO)₄ Co moiety. The infrared spectrum of A was similarto that of B. The approximate amounts of A and B obtained were 1.6 and1.0 g, respectively. Analysis of B was consistent with the formulation[(CH₃)₃ NH]₅ (CO)₃ CoGe₂ W₁₁ SiO₄₀.

    ______________________________________                                        Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.5 (CO).sub.3 CoGe.sub.2            W.sub.11 SiO.sub.40 :                                                               C,     6.59;  H,   1.53; N,    2.13; O,  20.98;                               Co,    1.80;  Ge,  4.42; Si,   0.86                                     Found:                                                                              C,     6.37;  H,   1.36; N,    2.24; O,  21.39;                                      6.18        1.66        2.19      20.49                                                                         20.76                                Co,    1.92;  Ge,  4.03; Si,   0.93                                                  1.91        4.02        0.91                                     ______________________________________                                    

Bonding considerations require that the anion (OC)₃ CoGe₂ W₁₁ SiO₄₀ ⁵⁻actually be polymeric, [(OC)₃ CoGe₂ W₁₁ SiO₄₀ ⁵⁻ ]_(y). A small amountof A was dissolved in hot water. A gel formed as the solution cooled,which is also consistent with a polymeric structure for the product.Analysis by light scattering indicated a molecular weight of about 10⁶,corresponding to a value of y of about 330.

EXAMPLE 26 [(CH₃)₃ NH]₄ [(C₆ H₅)₃ P]₂ (C₇ H₈)RhSnW₁₁ PO₃₉

[(CH₃)₃ NH]₄ (C₇ H₈)₂ RhSnW₁₁ PO₃₉ (3.0 g; Ex. 23) was heated inrefluxing acetonitrile (100 ml). Water was added slowly until a clearsolution formed. This required 25 ml of water. Triphenylphosphine (1.5g) was added. The solution became dark brown immediately and a brown-redsolid separated within a minute. Refluxing was continued for 8 minutes;the mixture was then filtered while still hot. The solid was driedovernight at ambient temperature in vacuum. It was washed thoroughlywith methylene chloride and re-dried. The yield was 2.7 g. Proton nmranalysis was consistent with the [(CH₃)₃ NH]₄ [(C₆ H₅)₃ P]₂ (C₇H₈)RhSnW₁₁ PO₃₉ formulation; the spectrum displayed aryl, bridgehead,olefinic, methyl and methylene protons in ratios 15:1:1.7:17:0.7compared to calculated ratios of 15:1:2:18:1.

    ______________________________________                                          Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.4 [(C.sub.6 H.sub.5).sub.3       P].sub.2 C.sub.7 H.sub.8 -                                                    RhSnW.sub.11 PO.sub.39 :                                                            C,     17.58;  H,   2.09;                                                                              N,    1.49;                                                                              O,  16.61;                                Rh,    2.74;   Sn,  3.26;                                                                              H.sub.2 O,                                                                          0.0                                      Found:                                                                              C,     18.20;  H,   2.23;                                                                              N,    1.41;                                                                              O,  16.02;                                       18.07        2.25       1.43     15.74                                 Rh,    0.93;   Sn,  3.12;                                                                              H.sub.2 O,                                                                          0.49                                                  1.10         3.05                                                ______________________________________                                    

EXAMPLE 27 [(CH₃)₃ NH]₁₁ π-C₃ H₅ Pd(SnW₁₁ SiO₃₉)₂ [(CH₃)₃ NH]₅ (C₆ H₅)₃P(π-C₃ H₅)PdSnW₁₁ SiO₃₉

A. A solution of (C₆ H₅)₃ P(π-C₃ H₅)PdSnCl₃ (3.0 g) in tetrahydrofuran(30 ml) was prepared in a nitrogen atmosphere and then added in air to asolution of K₈ W₁₁ SiO₃₉.10H₂ O (10.5 g) in water (75 ml) at 60°. Themixture was maintained at 60° for ten minutes, allowed to cool, andfiltered. The filtrate was diluted with water (50 ml) and refilteredthrough diatomaceous earth. Excess trimethylammonium chloride was addedto the filtrate to precipitate a near-white solid. This mixture wasfiltered to isolate an off-white solid (A) and obtain a yellow filtrate,from which 2.3 g of bright-yellow crystalline [(CH₃)₃ NH]₁₁ π-C₃ H₅Pd(SnW₁₁ SiO₃₉)₂ slowly separated.

    ______________________________________                                        Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.11 C.sub.3 H.sub.5 Pd(SnW.sub.1    1 SiO.sub.39).sub.2 :                                                               C,     6.76;  H,   1.81; N,    2.40;                                                                              O,  19.5;                                 Pd,    1.66;  Si,  0.88; Sn,   3.71                                     Found:                                                                              C,     6.79;  H,   1.82; N,    2.28;                                                                              O,  18.71;                                       6.72        1.89        2.29                                           Pd,    1.74;  Si,  0.93; Sn,   3.73                                                  1.71        0.92        3.68                                     ______________________________________                                    

Proton nuclear magnetic resonance analysis confirmed the presence of theallyl group and the absence of triphenylphosphine. The allyl:methylproton ratio was correct for the above composition.

B. The process of part A was repeated except that it was conductedentirely in a nitrogen atmosphere. This did not appear to change theresults. The off-white solid (6.0 g) corresponding to solid A in thepreceding reaction was analyzed and found to be a mixture ofapproximately one-third [(CH₃)₃ NH]₁₁ π-C₃ H₅ Pd(SnW₁₁ SiO₃₉)₂ andtwo-thirds [(CH₃)₃ NH]₅ (C₆ H₅)₃ P(π-C₃ H₅)PdSnW₁₁ SiO₃₉.

    ______________________________________                                          Anal. Calc'd for mixture as specified: C, 10.46;                            H, 1.94; N, 2.13; Pd, 2.57; Sn, 3.50                                          Found:                                                                              C,     10.65;  H,   2.05; N,  2.10;                                                                              Pd,   2.49;                                       10.94        2.08      2.15       2.43                                 Sn,    3.53                                                                          3.58                                                             ______________________________________                                    

Proton nmr analysis of this mixture revealed a phenyl:allyl:methyl groupratio of 2.2:0.9:21 compared with 2:1:21 calculated for the mixture.

Other palladium-containing compounds similar to the first product of theforegoing example can be made by suitable variations in the proceduredescribed therein. These include H₉ π-C₃ H₅ Pd(SnW₁₁ PO₃₉)₂, Na₁₁ π-C₃H₅ Pd(SnW₁₁ GeO₃₉)₂, and K₁₁ π-C₃ H₅ Pd(SnMo₁₁ SiO₃₉)₂.

EXAMPLE 28 [(CH₃)₃ NH]₄ [π-C₅ H₅ Fe(CO)₂ Ge]₂ Mo₁₁ SiO₄₀

A solution of lithium acetate (12 g) in water (100 ml) was brought to pH5.5 with acetic acid. Fifteen grams of Na₄ Mo₁₂ SiO₄₀ hydrate was added.The solution was stirred for ten minutes and then filtered. The filtratewas warmed to 55° and a warm solution of π-C₅ H₅ Fe(CO)₂ GeCl₃ (7.0 g)in methanol (45 ml) was added. The solution was then heated to 60° andallowed to cool. The major portion of the reaction mixture was thenfiltered, allowed to stand for thirteen days, and refiltered.Trimethylammonium chloride (0.5 g) was added to the filtrate toprecipitate a greenish-yellow solid. The major portion of this waswashed with water at ambient temperature and then dried overnight invacuum at room temperature. It consisted of 1.2 g of [(CH₃)₃ NH]₄ [π-C₅H₅ Fe(CO)₂ Ge]₂ Mo₁₁ SiO₄₀.

    ______________________________________                                          Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.4 [π-C.sub.5 H.sub.5          Fe(CO).sub.2 -                                                                Ge].sub.2 Mo.sub.11 SiO.sub.40 :                                                    C,     12.68;  H,   2.05; N,  2.27; Fe,  4.53;                                Ge,    5.89;   O,   28.58                                               Found:                                                                              C,     11.92;  H,   1.87; N,  2.03; Fe,  5.26;                                       12.11        1.94      2.00       4.84                                 Ge,    6.04;   O,   28.46                                                            5.85         29.19                                                                         28.59                                               ______________________________________                                    

The proton nmr spectrum had a methyl-to-cyclopentadienyl proton ratio of4.2:1 (calc'd for above salt: 3.6:1). The infrared spectrum wasconsistent with the formulation, exhibiting C.tbd.O and molybdosilicateabsorption bands.

EXAMPLE 29 K₅ [(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnW₁₁ SiO₃₉

A solution of [(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnCl₃ (0.97 g) in tetrahydrofuran(10 ml) was added to a solution of K₈ W₁₁ SiO₃₉.10H₂ O (3.2 g) in water(40 ml) at 60° C. The resulting mixture was stirred for 45 minutes andthen filtered. The filter cake was extracted with water (150 ml) at 55°C. The filtered extracts were allowed to cool and were then mixed with asolution of potassium nitrate (1.0 g) in water (10 ml). After thirtyminutes another one gram of potassium nitrate in water (10 ml) wasadded. After two more hours the mixture was filtered to obtain a hydrateof K₅ [(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnW₁₁ SiO₃₉. The remainder of theoriginal filter cake was then reextracted with boiling water (100 ml).The filtered extracts were mixed with a solution of potassium nitrate(2.0 g) in water (15 ml), allowed to stand for two hours and refiltered.This gave more of the same product obtained above. The combined yieldwas 1.5 g.

    ______________________________________                                          Anal. Calc'd for K.sub.5 [(C.sub.6 H.sub.5).sub.3 P].sub.2 Ir(CO)(H).sub    .2 SnW.sub.11 -                                                               SiO.sub.39 . 6 H.sub.2 O:                                                           C,     11.56;  H,   1.15;                                                                              K,   5.09; Sn,  3.09                           Found:                                                                              C,     12.35;  H,   1.32;                                                                              K,   5.14; Sn,  3.54                                        11.77        1.35      4.95       3.66                           ______________________________________                                    

The infrared spectrum, determined in a mineral-oil mull, exhibitedabsorptions at 2120 cm⁻¹ (Ir-H) and 2010 cm⁻¹ (C.tbd.O) as well as bandscharacteristic of water, coordinated triphenylphosphine, and the --SnW₁₁SiO₃₉ moiety. The proton nmr spectrum had resonances for the aromaticand for the hydride protons in an observed ratio of 17.2:1, compared toa calculated ratio of 15:1. The hydridic protons exhibited one resonanceat 21.2 (J_(P-H)(cis) =15 cps; J_(H-H) =4 cps) and one of equalintensity at 22 (J_(P-H)(trans) =108 cps; J_(P-H)(cis) =15 cps; J_(H-H)=4 cps).

The use of [(C₆ H₅)₃ P]₂ Ir(CO)(D)₂ SnCl₃, prepared according to thereference given above, in place of [(C₆ H₅)₃ P]₂ Ir(CO)(H)₂ SnCl₃ in asimilar experiment gave the corresponding deuteride.

EXAMPLE 30 [(CH₃)₃ NH]₅ [(C₂ H₅)₃ P]₂ Pt(H)SnW₁₁ SiO₃₉

A solution of K₈ W₁₁ SiO₃₉.10H₂ O (9.5 g) in water (75 ml) was preparedand heated to 60°-65°. A solution of 2.1 g of trans-[(C₂ H₅)₃ P]₂Pt(H)SnCl₃ ; Lindsey, Parshall, and Stolberg, J. Am. Chem. Soc., 87, 658(1967); in tetrahydrofuran (15 ml) was added. The mixture was stirredfor five minutes at 65° and then filtered while still hot. Excesstrimethylammonium chloride was added to the yellow filtrate toprecipitate a yellowish-green solid (8.0 g). The infrared spectrum(mineral-oil mull) of this solid had an absorption band at about 2090cm⁻¹, demonstrating retention of the Pt-H moiety. Part of this solid(5.4 g) was stirred in water (300 ml) at 40°-45° to obtain a turbidsolution which was filtered through diatomaceous earth. Successiveadditions of trimethylammonium chloride to the filtrate, each additionfollowed by filtration, gave three successive crops of yellow solid. Thelast crop was analyzed.

    ______________________________________                                          Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.5 [(C.sub.2 H.sub.5).sub.3       P].sub.2 Pt-                                                                  (H)SnW.sub.11 SiO.sub.39 :                                                              Pt,     5.53;     Sn,     3.37                                      Found:    Pt,     4.91;     Sn,     3.19                                                        5.13              3.12                                      ______________________________________                                    

EXAMPLE 31 [(CH₃)₃ NH]₄ [(C₂ H₅)₃ P]₂ Pt(H)SnW₁₁ PO₃₉

A solution of lithium acetate (15.0 g) in water (50 ml) was brought topH 5.5 with acetic acid. Tungstophosphoric acid (7 g) was added followedby a solution of trans-[(C₂ H₅)₃ P]₂ Pt(H)SnCl₃ (1.5 g) intetrahydrofuran (10 ml). The mixture was stirred for five minutes andthen filtered. The addition of excess trimethylammonium chloride to thefiltrate gave a precipitate containing a hydrate of [(CH₃)₃ NH]₄ [(C₂H₅)₃ P]₂ Pt(H)SnW₁₁ PO₃₉.

    ______________________________________                                          Anal. Calc'd for [(CH.sub.3).sub.3 NH].sub.4 [(C.sub.2 H.sub.5).sub.3       P].sub.2 Pt(H)-                                                               SnW.sub.11 PO.sub.39 . 4H.sub.2 O:                                                  C,     8.14;  H,   2.22;                                                                              N,   1.58; O,    19.43;                               Sn,    3.35;  Pt,  5.51;                                                                              H.sub.2 O,                                                                         2.03                                       Found:                                                                              C,     8.64;  H,   1.96;                                                                              N,   1.24; O,    19.47;                                      8.62        2.07      1.30        18.99                                                                         19.18                                Sn,    3.45;  Pt,  7.36;                                                                              H.sub.2 O,                                                                         2.09                                                    3.30        7.55      2.30                                       ______________________________________                                    

The infrared absorption spectrum (mineral-oil mull) exhibited a band atabout 2120 cm⁻¹, assignable to the Pt-H moiety

INDUSTRIAL APPLICABILITY

As shown in following Examples A, B, C, and D, the products of theinvention are catalysts for the oligomerization of terephthalic acidwith ethylene glycol. This oligomerization is an important step in thepreparation of commercial polyester. Examples B, C and D show that theproducts have significantly higher catalytic activity than thecommercially available heteropolyanionic compound of Example A.

EXAMPLE A (Control)

A mixture of terephthalic acid (41.5 g), ethylene glycol (31.0 g) andNa₄ W₁₂ SiO₄₀ (510.4 mg; commercial sample, probably hydrated) washeated at 240.8°-241° for six hours in such a fashion that the waterformed was removed by distillation. No clear oligomer was formed; theamount of water separated indicated 42% conversion to oligomer.

EXAMPLE B

Example A was repeated, with 520 mg of [(CH₃)₃ NH]₁₁ (CO)₃ Co(SnW₁₁SiO₃₉)₂. 3H₂ O in place of the Na₄ W₁₂ SiO₄₀. The temperature range was240.4°-241°. The amount of water formed indicated 91% conversion to anoligomer, which was cloudy pink in appearance.

EXAMPLE C

Example B was repeated with 520 mg of [(CH₃)₃ NH]₄ C₅ H₅ Fe(CO)₂ SnW₁₁PO₃₉ as a catalyst with a reaction time of 4.3 hours at 240.4°-241°. A90% conversion to a clear yellow oligomer was obtained.

EXAMPLE D

Example C was repeated with 500 mg of K₉ (CO)₃ Co(SnW₁₁ PO₃₉)₂.6H₂ O ascatalyst with a reaction period of 4.5 hours at a temperature of 240.8°to 241°. A clear colorless oligomer was obtained (83% conversion).

Examples E and F show that the novel heteropolyacids of the invention,which are made by cation-exchange from the salts, are catalysts for theisomerization of 1-butene, and for the dehydration of 2-butanol and thesubsequent isomerization of the 1-butane thus formed.

EXAMPLE E

An aqueous solution of [(CH₃)₃ NH]₄ [π-C₅ H₅ Fe(CO)₂ Fe]₂ W₁₁ SiO₄₀ (5g) was passed through an ion-exchange column containing an excess of acrosslinked poly(styrenesulfonic acid) cation exchange resin. Theeffluent was evaporated to dryness to leave an orange, glossy residuewhich was a hydrate of H₄ (π-C₅ H₅ Fe(CO)₂ GeOH)₂ W₁₁ SiO₃₉. Part ofthis (43 mg) was dissolved in ethanol. Silica (10 g, 750 sq meters/gsurface area) was added and the solution was evaporated to obtain theheteropolyacid supported on the silica. This product was dried one hourat 150° in vacuum. The resulting catalyst was then used as follows:

a. The catalyst (1 g) and toluene (10 ml) were stirred in a glasspressure bottle under 20-23 psig pressure of 1-butene at 60° for sevenhours. Gas chromatographic/mass spectrographic analysis indicated thatthe readily volatile fraction contained 96.8% of 1-butene, 1.2%cis-2-butene and 1.3% trans-2-butene. Better results were obtained in aflow system:

b. The same catalyst (3.0 g) was placed in a 3/4" diameter tube to forma catalyst bed 11/2" long. 1-Butene was passed through this bed at 60°at a flow rate of 20 ml/min. The effluent was found by gaschromatographic/mass spectrographic analysis to consist of 34% 1-butene;31% cis-2-butene and 35% trans-2-butene.

EXAMPLE F

2-Butanol (flow rate 1 ml/10 minutes) and nitrogen (flow rate 20ml/minute) were passed together through the catalyst recovered fromExample Eb, in the same reactor, for one hour at 150°. The effluent waspassed through an ambient temperature trap, which collected 1.25 g of amixture of butanol and water, and then through a trap cooled with solidcarbon dioxide. The latter trap condensed 4 ml of a liquid shown by gaschromatography to be a mixture of butenes, primarily cis and trans2-butene.

I claim:
 1. Salts and acids containing a triheteropolyanion in which oneaddenda atom of a heterododecatungstate or heterododecamolybdate isreplaced by one tin atom or by two germanium atoms, in which the tinatom or the germanium atoms are bonded to a ligated transition metal,the central atom of the heterododecaanion is not bonded directly to theligated transition metal-tin moiety or the ligated transitionmetal-germanium moiety, the added ligated transition metal is not partof the dodecanuclear cage structure, the heteropolyanion contains atleast one metal-metal bond which is outside the skeletal structure ofthe heteropolyanion, and the salts and acids are of a formula selectedfrom the group consisting of

    Q.sub.a L.sub.b MSnM'.sub.11 XO.sub.39                     ( 1)

    Q.sub.a L.sub.b-1 M(SnM'.sub.11 XO.sub.39).sub.2           ( 2)

    Q.sub.a (L.sub.b MGe).sub.2 M'.sub.11 XO.sub.40            ( 3)

    Q.sub.a L.sub.b M(GeOH).sub.2 M'.sub.11 XO.sub.39          ( 4)

    Q.sub.a L.sub.b M(SnM'.sub.11 XO.sub.39)(SnM".sub.11 X'O.sub.39) (5)

and

    {Q.sub.a L.sub.b-1 MGe.sub.2 M'.sub.11 XO.sub.40 }.sub.y   ( 6)

in which Q is one equivalent of a cation; L_(b) M is a ligatedtransition metal M bonded to b ligands L, b is at least 1, and theligands are the same or different when b is greater than 1; M' and M"are W or Mo; X and X' are Si, P, Co or Ge; with the proviso that atleast one of M" and X' is different from M' and X, respectively; a isthe number of formal negative charges on the heteropolyanion; and y isthe degree of polymerization.
 2. The salts and acids of claim 1 of theformula Q_(a) L_(b) MSnM'₁₁ XO₃₉.
 3. The salts and acids of claim 1 ofthe formula Q_(a) L_(b-1) M(SnM'₁₁ XO₃₉)₂.
 4. The salts and acids ofclaim 3 of the formula Q_(a) π-C₃ H₅ Pd(SnM'₁₁ XO₃₉)₂.
 5. The salts andacids of claim 4 of the formula Q_(a) π-C₃ H₅ Pd(SnW₁₁ XO₃₉)₂.
 6. Thesalts and acids of claim 5 of the formula Q_(a) π-C₃ H₅ Pd(SnW₁₁SiO₃₉)₂.
 7. The salts and acids of claim 1 of the formula Q_(a) (L_(b)MGe)₂ M'₁₁ XO₄₀.